Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a sparingly or non-ethoxylated fatty alcohol, a cationic surfactant, an alkaline agent and a reducing agent

ABSTRACT

The invention relates to a process for dyeing and/or lightening keratin fibres such as the hair, using i) at least one direct dye bearing a disulfide, thiol or protected-thiol function and ii) at least one sparingly or non-ethoxylated fatty alcohol, iii) at least one cationic surfactant, iv) at least one alkaline agent, and v) at least one reducing agent. The invention also relates to a composition comprising the ingredients i) to v), to the use of the combination of i), ii), iii), iv) and v) for the dyeing and/or lightening of keratin fibres, and to a multi-compartment kit comprising the ingredients i) to v). The dyeing process and the composition according to the invention especially afford a long-lasting coloration on keratin fibres, which is strong, chromatic and/or homogeneous, with or without the use of an oxidizing agent.

The invention relates to a process for dyeing and/or lightening keratin fibres using direct dyes.

It is known practice to dye keratin fibres by direct dyeing or semi-permanent dyeing. Direct dyeing or semi-permanent dyeing consists in introducing colour via a coloured molecule that becomes adsorbed onto the surface of the hair or that penetrates into the hair. Thus, the process conventionally used in direct dyeing consists in applying to keratin fibres direct dyes, which are coloured and colouring molecules that have affinity for the fibres, leaving the fibres in contact with the colouring molecules and then optionally rinsing the fibres. Generally, this technique leads to chromatic colorations.

Scientific research has been conducted for several years to modify the colour of keratin materials, especially keratin fibres, and in particular to mask white fibres, to modify the colour of the fibres permanently or temporarily, and to satisfy new desires and needs in terms of colours and durability.

Patent applications EP 1 647 580, WO 2005/097 051, EP 2 004 759, EP 2 075 289, WO 2007/110 541, WO 2007/110 540, WO 2007/110 539, WO 2007/110 538, WO 2007/110 537, WO 2007/110 536, WO 2007/110 535, WO 2007/110 534, WO 2007/110 533, WO 2007/110 532, WO 2007/110 531, EP 2 070 988, WO 2009/040 354 and WO 2009/034 059 disclose direct dyes bearing a disulfide, thiol or protected-thiol function, for dyeing the hair. The colours obtained are not sufficiently satisfactory, especially in terms of coloration intensity, colour selectivity between the root and the end, and chromaticity of the colour.

The aim of the present invention is to provide novel systems for dyeing the hair, even without the use of a chemical oxidizing agent, which make it possible to obtain improved colorations, especially in terms of fastness with respect to external agents, homogeneity of the coloration (little selectivity between the root and the end of the keratin fibres), and intensity, and/or which do not impair the cosmetic properties of the keratin fibres.

This aim is achieved with the present invention, a first subject of which is a cosmetic composition comprising:

-   i) at least one direct dye bearing a disulfide function, a thiol     function or a protected-thiol function, especially of formula (I):

A-(X)_(p)—C_(sat)—S—U  (I)

-   -   salts thereof with an organic or mineral acid, optical or         geometric isomers thereof, tautomers thereof, and solvates         thereof such as the hydrates,     -   in which formula (I):         -   U represents a radical chosen from:             -   a) —S—C′_(sat)—(X′)_(p′)-A′; and             -   b) —Y;         -   A and A′, which may be identical or different, represent a             radical containing at least one quaternized cationic             chromophore or at least one chromophore bearing a             quaternized or quaternizable cationic group;         -   Y represents i) a hydrogen atom; or ii) a thiol-function             protecting group;         -   X and X′, which may be identical or different, represent a             linear or branched, saturated or unsaturated divalent C₁-C₃₀             hydrocarbon-based chain, optionally interrupted and/or             optionally terminated at one or both of its ends with one or             more divalent groups or combinations thereof chosen from:             -   —N(R)—, —N⁺(R)(R)—, —O—, —S—, —CO—, —SO₂— with R, which                 may be identical or different, chosen from a hydrogen                 and a C₁-C₄ alkyl, hydroxyalkyl or aminoalkyl radical;             -   an aromatic or non-aromatic, saturated or unsaturated,                 fused or non-fused (hetero)cyclic radical optionally                 comprising one or more identical or different,                 optionally substituted heteroatoms;         -   p and p′, which may be identical or different, are equal to             0 or 1;         -   C_(sat) and C′_(sat), which may be identical or different,             represent an optionally substituted linear or branched, or             cyclic, C₁-C₁₈ alkylene chain;

-   ii) at least one sparingly ethoxylated or non-ethoxylated fatty     alcohol;

-   iii) at least one cationic surfactant; iv) at least one alkaline     agent; and

-   v) at least one reducing agent.

Another subject of the invention is a process for dyeing and/or lightening keratin fibres, especially dark keratin fibres, by applying to the said fibres the ingredients i) to v) as defined previously, the said ingredients being applied together or separately.

Another subject of the invention is the use of the composition comprising i), ii), iii), iv) and v) as defined previously, for the dyeing and/or lightening of keratin fibres.

Another subject of the invention is a multi-compartment kit comprising i), ii), iii), iv) and v) as defined previously.

The colorations obtained are attractive, aesthetic, intense, strong, chromatic and very fast or persistent with respect to common attacking factors or everyday assaults such as sun, sebum and especially with respect to perspiration, and other hair treatments such as successive shampooing, while at the same time respecting the keratin fibres. The intensity obtained is particularly noteworthy. The same is true for the colour homogeneity or selectivity of the colour.

For the purposes of the present invention, and unless otherwise indicated:

-   -   a “direct dye bearing a disulfide function” is a direct dye         comprising one or more cationic chromophores that absorb light         in the visible spectrum, and comprising a disulfide bond: —S—S—         between two carbon atoms and is preferably indirectly bonded to         the chromophore(s) of the dye, i.e. between the chromophores and         the —S—S— function there is at least one methylene group;     -   a “direct dye bearing a protected-thiol function” is a direct         dye comprising a chromophore, comprising a protected-thiol         function —SY in which Y is a protecting group known to those         skilled in the art, for instance those described in the         publications Protective Groups in Organic Synthesis, T. W.         Greene, John Wiley & Sons ed., NY, 1981, pp. 193-217; Protecting         Groups, P. Kocienski, Thieme, 3^(rd) ed., 2005, chap. 5; and         Ullmann's Encyclopedia, Peptide Synthesis, pp. 4-5, 2005         Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a19         157; it being understood that the said protected-thiol function         is preferably indirectly bonded to the chromophore of the dye,         i.e. between the chromophore and the function —SY there is at         least one methylene group;     -   a “direct dye bearing a thiol function” is a direct dye         comprising a chromophore, and comprising a thiol function —SY′         in which Y′ is i) a hydrogen atom; ii) an alkali metal; iii) an         alkaline-earth metal; iv) an ammonium group: N⁺R R R R or a         phosphonium group: P⁺R R R R with R, R, R and R, which may be         identical or different, representing a hydrogen atom or a group         (C₁-C₄)alkyl, preferentially comprising a thiol function —SH, it         being understood that the said thiol function is preferably         indirectly bonded to the chromophore of the dye, i.e. between         the chromophore and the function —SY′ there is at least one         methylene group;     -   a “chromophore” is a radical derived from a dye, i.e. a radical         derived from the molecule that absorbs light in the visible         radiation range that is visually perceptible by man, i.e. an         absorption wavelength λ_(abs) inclusively between 400 and 800         nm; the chromophore may be fluorescent, i.e. it is capable of         absorbing in the UV and visible radiation range at a wavelength         λ_(abs) inclusively between 250 and 800 nm and capable of         re-emitting in the visible range at an emission wavelength         λ_(em) inclusively between 400 and 800 nm;     -   a “chromophore” is said to be “quaternized cationic” or “bearing         a quaternized cationic group” if it comprises in its structure         at least one permanent cationic charge formed from at least one         quaternized nitrogen atom (ammonium) or quaternized phosphorus         atom (phosphonium), preferably nitrogen;     -   a group is said to be “bearing a quaternizable cationic group”         when it comprises in its structure at least one tertiary amine         or tertiary phosphine at the end of a hydrocarbon-based chain,         preferably C₁-C₁₀ alkyl, such as —(CR′R″)_(p)—N(R_(a))—R_(b)         with R′ and R″, which may be identical or different,         representing a hydrogen atom or a (C₁-C₆) alkyl group; R_(a) and         R_(b), which may be identical or different, representing a         (C₁-C₆)alkyl group, a monohydroxy(C₁-C₆)alkyl group, a         (poly)(hydroxy)(C₁-C₆)alkyl group or R_(a) and R_(b) form,         together with the nitrogen atom that bears them, a         heterocycloalkyl group such as morpholino, which, once         quaternized, will become morpholinium, piperidino, which, once         quaternized, will become piperidinium, or piperazino, which,         once quaternized, will become piperazinium; and p representing         an integer between 1 and 10 inclusive; preferably, R′ and R″         represent a hydrogen atom, R_(a) and R_(b) represent a         (C₁-C₄)alkyl group and p is between 2 and 5;     -   the dyes according to the invention contain one or more         chromophores, and these dyes are capable of absorbing light at a         wavelength λ_(abs) particularly of between 400 and 700 nm         inclusive;     -   the “fluorescent” dyes according to the invention are dyes         containing at least one fluorescent chromophore, and these dyes         are capable of absorbing in the visible range at a wavelength         λ_(abs) particularly inclusively between 400 and 800 nm and of         re-emitting in the visible range at a longer wavelength λ_(em)         than that absorbed, inclusively between 400 and 800 nm. The         difference between the absorption and emission wavelengths, also         known as the Stoke's shift, is inclusively between 1 nm and 100         nm. More preferentially, fluorescent dyes are dyes that are         capable of absorbing at a wavelength λ_(abs) inclusively between         420 and 550 nm and of re-emitting in the visible range at a         wavelength λ_(em) inclusively between 470 and 600 nm;     -   chromophores are said to be “different” when they differ in         their chemical structure and may be chromophores derived from         different families or from the same family on condition that         they have different chemical structures: for example, the         chromophores may be chosen from the family of azo dyes but         differ in the chemical structure of the radicals constituting         them or in the respective position of these radicals;     -   an “alkylene chain” represents a divalent acyclic C₁-C₂₀         hydrocarbon-based chain; particularly C₁-C₆ and more         particularly C₁-C₂ when the chain is linear; optionally         substituted with one or more groups, which may be identical or         different, chosen from i) hydroxyl, ii) (C₁-C₂)alkoxy, iii)         (poly)hydroxy(C₂-C₄)alkoxy(di)(C₁-C₂)(alkyl)amino, iv)         R^(a)—Z^(a)—C(Z^(b))—Z^(c)—, and v) R^(a)—Z^(a)—S(O)_(t)—Z^(c)—         with Z^(a) and Z^(b), which may be identical or different,         representing an oxygen or sulfur atom, or a group NR^(a′),         Z^(c), representing a bond, an oxygen or sulfur atom, or a group         NR^(a); R^(a), representing an alkali metal, a hydrogen atom, an         alkyl group, or alternatively is absent if another part of the         cationic molecule and R^(a′) representing a hydrogen atom or an         alkyl group and t is equal to 1 or 2; more particularly, the         groups iv) are chosen from carboxylate —C(O)O⁻ or —C(O)OMetal         (metal=alkali metal), carboxyl —O(O)—OH, guanidino         H₂H—C(NH₂)—NH—, amidino H₂H—C(NH₂)—, (thio)ureo H₂N—C(O)—NH— and         H₂N—C(S)—NH—, aminocarbonyl —O(O)—NRa′₂ or aminothiocarbonyl         —C(S)—NRa′₂; carbamoyl Ra′—C(O)—NRa′ or thiocarbamoyl         Ra′—C(S)—NRa′— with Ra′, which may be identical or different,         representing a hydrogen atom or a (C₁-C₄)alkyl group;     -   an “optionally substituted, saturated or unsaturated C₁-C₃₀         divalent hydrocarbon-based chain” represents a hydrocarbon-based         chain, particularly of C₁-C₈, optionally comprising one or more         conjugated or unconjugated double bonds, and in particular the         hydrocarbon-based chain is saturated; the said chain is         optionally substituted with one or more groups, which may be         identical or different, chosen from i) hydroxyl, ii)         (C₁-C₂)alkoxy, iii)         (poly)hydroxy(C₂-C₄)alkoxy(di)(C₁-C₂)(alkyl)amino, iv)         R^(a)—Z^(a)—C(Z^(b))—Z^(c)—, and v) R^(a)—Z^(a)—S(O)_(t)—Z^(c)—         with Z^(a) and Z^(b), which may be identical or different,         representing an oxygen or sulfur atom, or a group NR^(a)′,         Z^(c), representing a bond, an oxygen or sulfur atom, or a group         NR^(a); R^(a), representing an alkali metal, a hydrogen atom, an         alkyl group, or alternatively is absent if another part of the         cationic molecule and R^(a)′ representing a hydrogen atom or an         alkyl group and t is equal to 1 or 2; more particularly, the         groups iv) are chosen from carboxylate —O(O)O⁻ or —O(O)OMetal         (metal=alkali metal), carboxyl —O(O)—OH, guanidino         H₂H—C(NH₂)—NH—, amidino H₂H—C(NH₂)—, (thio)ureo H₂N—C(O)—NH— and         H₂N—C(S)—NH—, aminocarbonyl —O(O)—NRa′₂ or aminothiocarbonyl         —C(S)—NRa′₂; carbamoyl Ra′—C(O)—NRa′— or thiocarbamoyl         Ra′—C(S)—NRa′— with Ra′, which may be identical or different,         representing a hydrogen atom or a (C₁-C₄)alkyl group;     -   an “optionally substituted, saturated or unsaturated C₁-C₃₀         divalent hydrocarbon-based chain” represents a hydrocarbon-based         chain, particularly of C₁-C₈, optionally comprising one or more         conjugated or unconjugated double bonds, and in particular the         hydrocarbon-based chain is saturated; the said chain is         optionally substituted with one or more groups, which may be         identical or different, chosen from i) hydroxyl, ii)         (C₁-C₂)alkoxy, iii)         (poly)hydroxy(C₂-C₄)alkoxy(di)(C₁-C₂)(alkyl)amino, iv)         R^(a)—Z^(a)—C(Z^(b))—Z^(c)—, and v) R^(a)—Z^(a)—S(O)_(t)—Z^(c)—         with Z^(a) and Z^(b), which may be identical or different,         representing an oxygen or sulfur atom, or a group NR^(a)′,         Z^(c), representing a bond, an oxygen or sulfur atom, or a group         NR^(a); R^(a), representing an alkali metal, a hydrogen atom, an         alkyl group, or alternatively is absent if another part of the         cationic molecule and R^(a)′ representing a hydrogen atom or an         alkyl group and t is equal to 1 or 2; more particularly, the         groups iv) are chosen from carboxylate —C(O)O⁻ or —C(O)OMetal         (metal=alkali metal), carboxyl —O(O)—OH, guanidino         H₂H—C(NH₂)—NH—, amidino H₂H—C(NH₂)—, (thio)ureo H₂N—C(O)—NH— and         H₂N—C(S)—NH—, aminocarbonyl —C(O)—NRa′₂ or aminothiocarbonyl         —C(S)—NRa′₂; carbamoyl Ra′—C(O)—NRa′— or thiocarbamoyl         Ra′—C(S)—NRa′— with Ra′, which may be identical or different,         representing a hydrogen atom or a (C₁-C₄)alkyl group;     -   the “aryl” or “heteroaryl” radicals or the aryl or heteroaryl         part of a radical may be substituted with at least one         substituent borne by a carbon atom, chosen from:         -   a C₁-C₁₆ and preferably C₁-C₈ alkyl radical optionally             substituted with one or more radicals chosen from hydroxyl,             C₁-C₂ alkoxy, C₂-C₄ (poly)hydroxyalkoxy, acylamino, amino             substituted with two C₁-C₄ alkyl radicals, which may be             identical or different, optionally bearing at least one             hydroxyl group, or the two radicals possibly forming, with             the nitrogen atom to which they are attached, a saturated or             unsaturated, optionally substituted 5- to 7-membered and             preferably 5- or 6-membered heterocycle optionally             comprising another heteroatom identical to or different from             nitrogen;         -   a halogen atom;         -   a hydroxyl group;         -   a C₁-C₂ alkoxy radical;         -   a C₂-C₄ (poly)hydroxyalkoxy radical;         -   an amino radical;         -   a 5- or 6-membered heterocycloalkyl radical;         -   an optionally cationic 5- or 6-membered heteroaryl radical,             preferentially imidazolium, optionally substituted with a             (C₁-C₄)alkyl radical, preferentially methyl;         -   an amino radical substituted with one or two identical or             different C₁-C₆ alkyl radicals, optionally bearing at least:             -   i) a hydroxyl group,             -   ii) an amino group optionally substituted with one or                 two optionally substituted C₁-C₃ alkyl radicals, the                 said alkyl radicals possibly forming with the nitrogen                 atom to which they are attached a saturated or                 unsaturated, optionally substituted 5- to 7-membered                 heterocycle, optionally comprising at least one other                 heteroatom identical to or different from nitrogen,             -   iii) a quaternary ammonium group —N⁺R′R″R′″, M⁻ for                 which R′, R″ and R′″, which may be identical or                 different, represent a hydrogen atom or a C₁-C₄ alkyl                 group; and M⁻ represents the counterion of the organic                 or mineral acid or of the corresponding halide;             -   iv) an optionally cationic 5- or 6-membered heteroaryl                 radical, preferentially imidazolium, optionally                 substituted with a (C₁-C₄)alkyl radical, preferentially                 methyl;         -   an acylamino radical (—NR—C(O)—R′) in which the radical R is             a hydrogen atom or a C₁-C₄ alkyl radical optionally bearing             at least one hydroxyl group and the radical R′ is a C₁-C₂             alkyl radical;         -   a carbamoyl radical ((R)₂N—C(O)—) in which the radicals R,             which may be identical or different, represent a hydrogen             atom or a C₁-C₄ alkyl radical optionally bearing at least             one hydroxyl group;         -   an alkylsulfonylamino radical (R′—S(O)₂—N(R)—) in which the             radical R represents a hydrogen atom or a C₁-C₄ alkyl             radical optionally bearing at least one hydroxyl group and             the radical R′ represents a C₁-C₄ alkyl radical, or a phenyl             radical;         -   an aminosulfonyl radical ((R)₂N—S(O)₂—) in which the             radicals R, which may be identical or different, represent a             hydrogen atom or a C₁-C₄ alkyl radical optionally bearing at             least one hydroxyl group;         -   a carboxylic radical in acid or salified form (preferably             with an alkali metal or a substituted or unsubstituted             ammonium);         -   a cyano group;         -   a nitro or nitroso group;         -   a polyhaloalkyl group, preferentially trifluoromethyl;     -   the cyclic or heterocyclic part of a non-aromatic radical may be         substituted with at least one substituent chosen from the         following groups:         -   hydroxyl;         -   C₁-C₄ alkoxy, C₂-C₄ (poly)hydroxyalkoxy,         -   (C₁-C₄)alkyl;         -   alkylcarbonylamino (R—C(O)—N(R′)—) in which the radical R′             is a hydrogen atom or a C₁-C₄ alkyl radical optionally             bearing at least one hydroxyl group, and the radical R is a             C₁-C₂ alkyl radical or an amino radical optionally             substituted with one or two C₁-C₄ alkyl groups, which may be             identical or different, themselves optionally bearing at             least one hydroxyl group, the said alkyl radicals possibly             forming, with the nitrogen atom to which they are attached,             a saturated or unsaturated, optionally substituted 5- to             7-membered heterocycle optionally comprising at least one             other nitrogen or non-nitrogen heteroatom;         -   alkylcarbonyloxy (R—C(O)—O—) in which the radical R is a             C₁-C₄ alkyl radical or an amino radical substituted with one             or two identical or different C₁-C₄ alkyl groups, themselves             optionally bearing at least one hydroxyl group, the said             alkyl radicals possibly forming with the nitrogen atom to             which they are attached a saturated or unsaturated,             optionally substituted 5- to 7-membered heterocycle,             optionally comprising at least one other nitrogen or             non-nitrogen heteroatom;         -   alkoxycarbonyl (R-G-C(O)—) in which the radical R is a C₁-C₄             alkoxy radical, G is an oxygen atom or an amino group             optionally substituted with a C₁-C₄ alkyl group optionally             bearing at least one hydroxyl group, the said alkyl radical             possibly forming, with the nitrogen atom to which they are             attached, a saturated or unsaturated, optionally substituted             5- to 7-membered heterocycle, optionally comprising at least             one other nitrogen or non-nitrogen heteroatom;     -   a cyclic or heterocyclic radical, or a non-aromatic portion of         an aryl or heteroaryl radical, may also be substituted with one         or more oxo groups;     -   a hydrocarbon-based chain is unsaturated when it comprises one         or more double bonds and/or one or more triple bonds;     -   an “aryl” radical represents a fused or non-fused monocyclic or         polycyclic carbon-based group containing from 6 to 22 carbon         atoms, and in which at least one ring is aromatic;         preferentially, the aryl radical is a phenyl, biphenyl,         naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;     -   a “heteroaryl radical” represents a fused or non-fused,         optionally cationic, 5- to 22-membered monocyclic or polycyclic         group, comprising from 1 to 6 heteroatoms chosen from nitrogen,         oxygen, sulfur and selenium, and at least one ring of which is         aromatic; preferentially, a heteroaryl radical is chosen from         acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl,         benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl,         benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl,         imidazopyridyl, imidazolyl, indolyl, isoquinolyl,         naphthoimidazolyl, naphthoxazolyl, naphthopyrazolyl,         oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl,         pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl,         pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl,         thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl,         thiopyrylyl, triazolyl, xanthyl and the ammonium salt thereof;     -   a “heterocyclic radical” or “heterocycle” is a fused or         non-fused, 5- to 22-membered monocyclic or polycyclic         non-aromatic radical, comprising from 1 to 6 heteroatoms chosen         from nitrogen, oxygen, sulfur and selenium;     -   a “heterocycloalkyl radical” is a heterocyclic radical         comprising at least one saturated ring;     -   a “cationic heteroaryl radical” is a heteroaryl group as defined         previously, which comprises a quaternized endocyclic or         exocyclic cationic group,         -   when the cationic charge is endocyclic, it is included in             the electron delocalization via the mesomeric effect, for             example it is a pyridinium, imidazolium or indolinium group;

-   -   -   with R and R′ being a heteroaryl substituent as defined             previously and particularly a (hydroxy)(C₁-C₈)alkyl group             such as methyl;         -   when the cationic charge is exocyclic, for example, it is an             ammonium or phosphonium substituent R⁺ such as             trimethylammonium, which is outside the heteroaryl such as             pyridyl, indolyl, imidazolyl or naphthalimidyl in question;

-   -   -   with R being a heteroaryl substituent as defined previously             and R′ an ammonium R_(a)R_(b)R_(c)N⁺—, phosphonium             R_(a)R_(b)R_(c)P⁺— or ammonium             R_(a)R_(b)R_(c)N⁺—(C₁-C₆)alkylamino group with R_(a), R_(b)             and R_(c), which may be identical or different, representing             a hydrogen atom or a (C₁-C₈) alkyl group such as methyl;

    -   the term “cationic aryl bearing an exocyclic charge” means an         aryl ring whose quaternized cationic group is outside the said         ring: it is especially an ammonium or phosphonium substituent R⁺         such as trimethylammonium, outside the aryl such as phenyl or         naphthyl:

-   -   an “alkyl radical” is a linear or branched C₁-C₂₀ and preferably         C₁-C₈ hydrocarbon-based radical;     -   an “alkenylene radical” is an unsaturated hydrocarbon-based         divalent radical as defined previously, which may contain from 1         to 4 conjugated or unconjugated double bonds —C═C—; the         alkenylene group particularly contains 1 or 2 unsaturations;     -   the term “optionally substituted” attributed to the alkyl         radical means that the said alkyl radical may be substituted         with one or more radicals chosen from the following radicals: i)         hydroxyl, ii) C₁-C₄ alkoxy, iii) acylamino, iv) amino optionally         substituted with one or two identical or different C₁-C₄ alkyl         radicals, the said alkyl radicals possibly forming with the         nitrogen atom that bears them a 5- to 7-membered heterocycle,         optionally comprising another heteroatom identical to or         different from nitrogen; v) or a quaternary ammonium group         —N⁺R′R″R′″, M⁻ for which R′, R″ and which may be identical or         different, represent a hydrogen atom or a C₁-C₄ alkyl group, or         else —N⁺R′R″R′″, forms a heteroaryl such as imidazolium         optionally substituted with a C₁-C₄ alkyl group, and M⁻         represents the counterion of the organic or mineral acid or of         the corresponding halide;     -   an “alkoxy” radical is an alkyl-oxy radical for which the alkyl         radical is a linear or branched C₁-C₁₆ and preferentially C₁-C₈         hydrocarbon-based radical;     -   when the alkoxy group is optionally substituted, this implies         that the alkyl group is optionally substituted as defined         hereinabove;     -   the “tone depth” is the unit known to hairstyling professionals,         published in the book Sciences des traitements capillaires [Hair         treatment sciences] by Charles Zviak, 1988, published by Masson,         pp. 215 and 278; the tone depths range from 1 (black) to 10         (very light blond), one unit corresponding to one tone; the         higher the figure, the lighter the shade;     -   a “dark” keratin fibre is a keratin fibre whose lightness L*         measured in the CIEL L*a*b* system is less than or equal to 45         and preferably less than or equal to 40, given that L*=0 is         equivalent to black and L*=100 is equivalent to white;     -   “naturally or artificially dark hair” means hair whose tone         depth is less than or equal to 6 (dark blond) and preferably         less than or equal to 4 (chestnut-brown). Artificially dyed hair         is hair whose colour has been modified by a coloration         treatment, for example a coloration with direct dyes or         oxidation dyes;     -   the term “thickening polymer” means a polymer which, when         introduced at 1% by weight in an aqueous solution or an         aqueous-alcoholic solution containing 30% ethanol, and at pH 7,         or in an oil chosen from liquid petroleum jelly, isopropyl         myristate or cyclopentadimethylsiloxane, makes it possible to         achieve a viscosity of at least 100 cps and preferably of at         least 500 cps, at 25° C. and at a shear rate of 1 s⁻¹. This         viscosity may be measured using a cone/plate viscometer (Haake         R600 rheometer or the like). The thickening polymers may thicken         the aqueous phase and/or the fatty phase, preferentially the         aqueous phase.     -   The term “fatty alcohols” means saturated or unsaturated, linear         or branched fatty alcohols comprising between 8 and 200 carbon         atoms, preferably C₈-C₄₀.     -   The term “sparingly ethoxylated” fatty alcohol means a fatty         alcohol comprising from 1 to 6 ethylene oxide units and         preferably from 1 to 3 ethylene oxide units per molecule;     -   an “organic or mineral acid salt” is more particularly chosen         from salts chosen from a salt derived from i) hydrochloric acid         HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H₂SO₄, iv)         alkylsulfonic acids: Alk-S(O)₂OH such as methanesulfonic acid         and ethanesulfonic acid; v) arylsulfonic acids: Ar—S(O)₂OH such         as benzenesulfonic acid and toluenesulfonic acid; vi) citric         acid; vii) succinic acid; viii) tartaric acid; ix) lactic         acid; x) alkoxysulfinic acids: Alk-O—S(O)OH such as         methoxysulfinic acid and ethoxysulfinic acid; xi)         aryloxysulfinic acids such as tolueneoxysulfinic acid and         phenoxysulfinic acid; xii) phosphoric acid H₃PO₄; xiii) acetic         acid CH₃C(O)OH; xiv) triflic acid CF₃SO₃H; and xv)         tetrafluoroboric acid HBF₄;     -   an “anionic counterion” means an anion or an anionic group         derived from an organic or mineral acid salt which         counterbalances the cationic charge of the dye; more         particularly, the anionic counterion is chosen from: i) halides         such as chloride or bromide; ii) nitrates; iii) sulfonates,         including C₁-C₆ alkylsulfonates: Alk-S(O)₂O⁻ such as         methanesulfonate or mesylate and ethanesulfonate; iv)         arylsulfonates: Ar—S(O)₂O⁻ such as benzenesulfonate and         toluenesulfonate or tosylate; v) citrate; vi) succinate; vii)         tartrate; viii) lactate; ix) alkyl sulfates: Alk-O—S(O)O⁻ such         as methyl sulfate and ethyl sulfate; x) aryl sulfates:         Ar—O—S(O)O⁻ such as benzene sulfate and toluene sulfate; xi)         alkoxy sulfates: Alk-O—S(O)₂O⁻ such as methoxy sulfate and         ethoxy sulfate; xii) aryloxy sulfates: Ar—O—S(O)₂O⁻, xiii)         phosphates O═P(OH)₂—O⁻, O═P(O⁻)₂—OH O═P(O⁻)₃,         HO—[P(O)(O⁻)]_(w)—P(O)(O⁻)₂ with w being an integer; xiv)         acetate; xv) triflate; and xvi) borates such as         tetrafluoroborate, xvii) disulfate (O═)₂S(O⁻)₂ or SO₄ ²⁻ and         monosulfate HSO₄ ⁻;     -   the anionic counterion, derived from the organic or mineral acid         salt, ensures the electrical neutrality of the molecule; thus,         it is understood that when the anion comprises several anionic         charges, then the same anion may serve for the electrical         neutrality of several cationic groups in the same molecule or         else may serve for the electrical neutrality of several         molecules; for example, a disulfide dye of formula (I) which         contains two cationic chromophores may contain either two         “singly charged” anionic counterion or a “doubly charged”         anionic counterion such as (O═)₂S(O⁻)₂ or O═P(O⁻)₂—OH;     -   moreover, the addition salts that may be used in the context of         the invention are especially chosen from addition salts with a         cosmetically acceptable base such as basifying agents as defined         below, for instance alkali metal hydroxides such as sodium         hydroxide, potassium hydroxide, aqueous ammonia, amines or         alkanolamines;     -   the term “at least one” is equivalent to the term “one or more”;         and     -   the term “inclusive” for a range of concentrations means that         the limits of that range are included in the defined range.

1). THE COMPOSITION OF THE INVENTION

The composition according to the invention is cosmetic, i.e. it is in a cosmetic medium and comprises:

-   -   i) at least one cationic direct dye bearing a disulfide         function, a thiol function or a protected-thiol function;     -   ii) at least one sparingly ethoxylated or non-ethoxylated fatty         alcohol;     -   iii) at least one cationic surfactant;     -   iv) at least one alkaline agent; and     -   v) at least one reducing agent

The Cosmetic Medium:

The term “cosmetic medium” means a medium that is suitable for dyeing keratin fibres, also known as a dye support, which is a cosmetic medium generally formed from water or a mixture of water and one or more organic solvents or a mixture of organic solvents. Preferably, the composition comprises water in a content especially inclusively between 5% and 95% relative to the total weight of the composition.

The term “organic solvent” means an organic substance that is capable of dissolving another substance without chemically modifying it.

Organic Solvents:

Examples of organic solvents that may be mentioned include C₁-C₄ lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

The organic solvents are preferably present in proportions preferably inclusively between 0.1% and 40% by weight approximately relative to the total weight of the dye composition, more preferentially between 1% and 30% by weight approximately and even more particularly inclusively between 5% and 25% by weight relative to the total weight of the composition.

i) Direct Dyes Bearing a Disulfide or Thiol Function of the Invention:

The direct dye(s) bearing a disulfide, thiol or protected-thiol function used in the invention are of formula (I) as defined previously.

According to one particular mode of the invention, the dyes (I) are disulfide dyes, i.e. for which U represents the following radical a) —S—C′_(sat)—(X′)_(p′)-A′, and more particularly the dyes of formula (I) are symmetrical, i.e. they are such that A=A′, C_(sat)=C′_(sat), X=X′ and p=p′.

According to another particular mode of the invention, the dyes of formula (I) bearing a thiol function are as defined previously, i.e. U representing the radical b) Y.

Another particular embodiment of the invention relates to fluorescent dyes bearing a disulfide, thiol or protected-thiol function.

i). 1) Y:

According to one particular embodiment of the invention, the direct dye of formula (I) is a thiol dye, i.e. Y represents i) a hydrogen atom.

In accordance with another particular embodiment of the invention, in the abovementioned formula (I), Y is a protecting group known to those skilled in the art, for instance those described in the publications “Protective Groups in Organic Synthesis”, T. W. Greene, published by John Wiley & Sons, NY, 1981, pp. 193-217; “Protecting Groups”, P. Kocienski, Thieme, 3rd edition, 2005, chapter 5, and Ullmann's Encyclopedia, “Peptide Synthesis”, pp. 4-5, 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a19 157;

In particular, Y represents a thiol-function protecting group chosen from the following radicals:

-   -   (C₁-C₄)alkylcarbonyl;     -   (C₁-C₄)alkylthiocarbonyl;     -   (C₁-C₄)alkoxycarbonyl;     -   (C₁-C₄)alkoxythiocarbonyl;     -   (C₁-C₄)alkylthio-thiocarbonyl;     -   (di)(C₁-C₄)(alkyl)aminocarbonyl;     -   (di)(C₁-C₄)(alkyl)aminothiocarbonyl;     -   arylcarbonyl, for instance phenylcarbonyl;     -   aryloxycarbonyl;     -   aryl(C₁-C₄)alkoxycarbonyl;     -   (di)(C₁-C₄)(alkyl)aminocarbonyl, for instance         dimethylaminocarbonyl;     -   (C₁-C₄)(alkyl)arylaminocarbonyl;     -   carboxyl;     -   SO₃ ⁻; M⁺ with M⁺ representing an alkali metal such as sodium or         potassium, or alternatively a counterion of the cationic         chromophore A and M⁺ are absent;     -   optionally substituted aryl such as phenyl, dibenzosuberyl or         1,3,5-cycloheptatrienyl;         -   optionally substituted heteroaryl; especially including the             following cationic or non-cationic heteroaryl radicals             comprising from 1 to 4 heteroatoms:             -   i) 5-, 6- or 7-membered monocyclic radicals such as                 furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or                 thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl,                 isoxazolium, thiazolyl, thiazolium, isothiazolyl,                 isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium,                 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl,                 1,2,4-oxazolium, 1,2,4-thiadiazolyl,                 1,2,4-thiadiazolium, pyrylium, thiopyridyl, pyridinium,                 pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium,                 pyridazinyl, pyridazinium, triazinyl, triazinium,                 tetrazinyl, tetrazinium, azepine, azepinium, oxazepinyl,                 oxazepinium, thiepinyl, thiepinium, imidazolyl,                 imidazolium;             -   ii) 8- to 11-membered bicyclic radicals such as indolyl,                 indolinium, benzimidazolyl, benzimidazolium,                 benzoxazolyl, benzoxazolium, di hydrobenzoxazolinyl,                 benzothiazolyl, benzothiazolium, pyridoimidazolyl,                 pyridoimidazolium, thienocycloheptadienyl, these                 monocyclic or bicyclic groups being optionally                 substituted with one or more groups such as                 (C₁-C₄)alkyl, for instance methyl, or                 polyhalo(C₁-C₄)alkyl, for instance trifluoromethyl;             -   iii) or the following tricyclic ABC radical:

-   -   -   -   in which the two rings A and C optionally comprise a                 heteroatom, and ring B is a 5-, 6- or 7-membered ring,                 particularly a 6-membered ring, and contains at least                 one heteroatom, for instance piperidyl or pyranyl;

        -   optionally cationic, optionally substituted             heterocycloalkyl, the heterocycloalkyl group especially             represents a saturated or partially saturated 5-, 6- or             7-membered monocyclic group comprising from 1 to 4             heteroatoms chosen from oxygen, sulfur and nitrogen, such as             di/tetrahydrofuryl, di/tetrahydrothiophenyl,             di/tetrahydropyrrolyl, di/tetrahydropyranyl,             di/tetra/hexahydrothiopyranyl, dihydropyridyl, piperazinyl,             piperidinyl, tetramethylpiperidyl, morpholinyl,             di/tetra/hexahydroazepinyl, di/tetrahydropyrimidinyl, these             groups being optionally substituted with one or more groups             such as (C₁-C₄) alkyl, oxo or thioxo; or the heterocycle             represents the following group:

-   -   -   in which R′^(c), R′^(f), R′^(g) and R′^(h), which may be             identical or different, represent a hydrogen atom or a             (C₁-C₄) alkyl group, or alternatively two groups R′^(g) with             R′^(h), and/or R′^(e) with R′^(f), form an oxo or thioxo             group, or alternatively R′^(g) with R′^(e) together form a             cycloalkyl; and v represents an integer between 1 and 3             inclusive; preferentially, R′^(c) to R′^(h) represent a             hydrogen atom; and An′″⁻ represents a counterion;         -   —C(NR′^(c)R′^(d))═N⁺R′^(e)R′^(f); An′″⁻ with R′^(c), R′^(d),             R′^(e) and R′^(f), which may be identical or different,             representing a hydrogen atom or a (C₁-C₄)alkyl group;             preferentially, R′^(c) to R′^(f) represent a hydrogen atom;             and An′″⁻ represents a counterion;         -   —C(NR′^(c)R′^(d))═NR′^(e); with R′^(c), R′^(d) and R′^(e) as             defined previously;         -   optionally substituted (di)aryl(C₁-C₄)alkyl such as             9-anthracenylmethyl, phenylmethyl or diphenylmethyl             optionally substituted with one or more groups especially             chosen from (C₁-C₄) alkyl, (C₁-C₄) alkoxy such as methoxy,             hydroxyl, alkylcarbonyl or (di)(C₁-C₄)(alkyl)amino such as             dimethylamino;         -   optionally substituted (di)heteroaryl(C₁-C₄)alkyl, the             heteroaryl group especially being a cationic or noncationic,             5- or 6-membered monocyclic radical comprising from 1 to 4             heteroatoms chosen from nitrogen, oxygen and sulfur, such as             pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such             as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium or             triazinyl groups, optionally substituted with one or more             groups such as alkyl, particularly methyl; advantageously,             the (di)heteroaryl(C₁-C₄)alkyl is (di)heteroarylmethyl or             (di)heteroarylethyl;         -   CR¹R²R³ with R¹, R² and R³, which may be identical or             different, representing a halogen atom or a group chosen             from:             -   (C₁-C₄)alkyl;             -   (C₁-C₄)alkoxy;             -   optionally substituted aryl such as phenyl optionally                 substituted with one or more groups, for instance                 (C₁-C₄)alkyl, (C₁-C₄)alkoxy or hydroxyl;             -   optionally substituted heteroaryl such as thiophenyl,                 furanyl, pyrrolyl, pyranyl or pyridyl, optionally                 substituted with a (C₁-C₄)alkyl group;             -   P(Z¹)R′¹R′²R′³ with R′¹ and R′², which may be identical                 or different, representing a hydroxyl, (C₁-C₄)alkoxy or                 alkyl group, R′³ representing a hydroxyl or                 (C₁-C₄)alkoxy group, and Z¹ representing an oxygen or                 sulfur atom;

    -   a sterically hindered ring; and

    -   optionally substituted alkoxyalkyl, such as methoxymethyl (MOM),         ethoxyethyl (EOM) and isobutoxymethyl.

According to one particular embodiment, the thiol-protected dyes of formula (I) comprise a group Y chosen from i) aromatic cationic 5- or 6-membered monocyclic heteroaryl comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, thiepinyl, thiepinium, imidazolium; ii) cationic 8- to 11-membered bicyclic heteroaryl such as indolinium, benzimidazolium, benzoxazolium, benzothiazolium, these monocyclic or bicyclic heteroaryl groups optionally being substituted with one or more groups such as alkyls, for instance methyl, or polyhalo(C₁-C₄)alkyl such as trifluoromethyl; iii) or the following heterocyclic:

in which R′^(c) and R′^(d), which may be identical or different, represent a hydrogen atom or a group (C₁-C₄)alkyl; preferentially R′^(c) to R′^(d) represent a group (C₁-C₄)alkyl such as methyl; and An′″⁻ represents a counterion.

In particular, Y represents a group chosen from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted with one or more (C₁-C₄)alkyl groups, especially methyl.

In particular, Y represents a protecting group such as:

-   -   (C₁-C₄)alkylcarbonyl, for instance methylcarbonyl or         ethylcarbonyl;     -   arylcarbonyl, for instance phenylcarbonyl;     -   (C₁-C₄)alkoxycarbonyl;     -   aryloxycarbonyl;     -   aryl(C₁-C₄)alkoxycarbonyl;     -   (di)(C₁-C₄)(alkyl)aminocarbonyl, for instance         dimethylaminocarbonyl;     -   (C₁-C₄)(alkyl)arylaminocarbonyl;     -   optionally substituted aryl such as phenyl;     -   5- or 6-membered monocyclic heteroaryl such as imidazolyl or         pyridyl;     -   cationic 5- or 6-membered monocyclic heteroaryl such as         pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium,         triazinium, imidazolium; these groups being optionally         substituted with one or more identical or different (C₁-C₄)alkyl         groups such as methyl;     -   cationic 8- to 11-membered bicyclic heteroaryl such as         benzimidazolium or benzoxazolium; these groups being optionally         substituted with one or more identical or different (C₁-C₄)alkyl         groups such as methyl;     -   cationic heterocycle having the following formula:

-   -   —C(NH₂)═N⁺H₂; An′″⁻; with An′″⁻ being an anionic counterion as         defined previously;     -   —C(NH₂)═NH;     -   SO₃ ⁻, M⁺ with M⁺ representing an alkali metal such as sodium or         potassium.

i). 2) C_(sat) and C′_(sat):

As indicated previously, in formula (I), C_(sat) and C′_(sat), independently of each other, represent a linear or branched or cyclic, optionally substituted C₁-C₁₈ alkylene chain. Substituents that may be mentioned include the following groups: i) amino, ii) (C₁-C₄)alkylamino, iii) (C₁-C₄)dialkylamino, or the group iv) R^(a)—Z^(a)—C(Z^(b))—Z^(c)—, in which Z^(a), Z^(b), which may be identical or different, represent an oxygen or sulfur atom, or a group NR^(a)′, Z^(c), representing a bond, an oxygen or sulfur atom or a group NR^(a) and R^(a), represents an alkali metal, a hydrogen atom or a C₁-C₄ alkyl group and R^(a)′ represents a hydrogen atom or a C₁-C₄ alkyl group; more particularly, the groups iv) are chosen from carboxylate —C(O)O⁻ or —C(O)OMetal (Metal=alkali metal), carboxyl —C(O)—OH, guanidino H₂H—C(NH₂)—NH—, amidino H₂H—C(NH₂)—, (thio)ureo H₂N—C(O)—NH— and H₂N—C(S)—NH—, aminocarbonyl —C(O)—NRa′₂ or aminothiocarbonyl —C(S)—NRa′₂; carbamoyl Ra′—C(O)—NRa′— or thiocarbamoyl Ra′—C(S)—NRa′— with Ra′, which may be identical or different, representing a hydrogen atom or a (C₁-C₄) alkyl group; the said substituent(s) are preferably present on the carbon in the beta or gamma position relative to the sulfur atoms of the disulfide, thiol or protected-thiol group.

Preferably, in the case of formula (I), C_(sat) and C′_(sat) represent a chain —(CH₂)_(k)— with k being an integer between 1 and 8 inclusive.

i). 3) X and X′:

In accordance with one particular embodiment of the invention, in the above-mentioned formula (I), when p and p′ is equal to 1, the radicals X and X′, which may be identical or different, represent the following sequence:

-(T)_(t)-(Z)_(z)-(T)_(t′)-

the said sequence being linked in formula (I) symmetrically as follows:

C_(sat) (or C′_(sat))-(T)_(t)-(Z)_(z)-(A or A′);

in which:

-   -   T and T′, which may be identical or different, represent one or         more radicals or combinations thereof chosen from: —O—; —S—;         —N(R)—; —N⁺(R)(R^(o))—; —S(O)—; —S(O)₂—; —C(O)—; with R, R^(o),         which may be identical or different, representing a hydrogen         atom, a C₁-C₄ alkyl radical, C₁-C₄ hydroxyalkyl radical or an         aryl(C₁-C₄)alkyl radical; and a cationic or non-cationic,         preferentially monocyclic heterocycloalkyl or heteroaryl         radical, preferentially containing two heteroatoms (more         preferentially two nitrogen atoms) and preferentially being 5-         to 7-membered, more preferentially imidazolium;     -   the indices t and t′, which may be identical or different, are         equal to 0 or 1;     -   Z represents:         -   —(CH₂)_(m)— radical with m being an integer between 1 and 8;         -   —(CH₂CH₂O)_(q)— or —(OCH₂CH₂)_(q)— in which q is an integer             between 1 and 5 inclusive;         -   an aryl, alkylaryl or arylalkyl radical in which the alkyl             radical is C₁-C₄ and the aryl radical is preferably C₆,             being optionally substituted with at least one group SO₃M             with M representing a hydrogen atom, an alkali metal or an             ammonium group substituted with one or more identical or             different, linear or branched C₁-C₁₈ alkyl radicals             optionally bearing at least one hydroxyl;     -   z is 0 or 1.

Moreover, according to one particular embodiment of the invention, Z represents:

in which M represents a hydrogen atom, an alkali metal or an ammonium group or an ammonium group substituted with one or more identical or different, linear or branched C₁-C₁₀ alkyl radicals optionally bearing at least one hydroxyl; 0-4 represents an integer between 0 and 4 inclusive, and q represents an integer inclusively between 1 and 6.

i). 4). A and A′:

The radicals A and/or A′ of formula (I) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group.

According to one preferred embodiment of the invention, the dyes (I) according to the invention are disulfides and comprise identical quaternized cationic chromophores A and A′

More particularly, the dyes of formula (I) according to the invention are symmetrical disulfides, i.e. they contain a C₂ axis of symmetry, i.e. formula (I) is such that:

A-(X)_(p)—C_(sat)—S—S—C′_(sat)—(X′)_(p′)-A′

with A=A′, X=X′, p=p′, C_(sat)=C′_(sat).

As chromophores that are useful, mention may be made of those derived from the following dyes: acridines; acridones; anthrapyrimidines; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanins such as azacarbocyanins, diazacarbocyanins, diazahemicyanins, hemicyanin, or tetraazacarbocyanins; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines such as dimethines of stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanin; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

Among the cationic azo chromophores, mention may be made particularly of those derived from the cationic dyes described in the Kirk Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & Sons, updated on 19 Apr. 2010.

Among the azo chromophores A and/or A′ that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954.

According to one preferred embodiment of the invention, the coloured chromophore A and/or A′ is chosen from cationic chromophores, preferentially those derived from dyes known as “basic dyes”.

Among the azo chromophores, mention may be made of those described in the Colour Index International 3rd edition, and especially the following compounds:

-   -   Basic Red 22     -   Basic Red 76     -   Basic Yellow 57     -   Basic Brown 16     -   Basic Brown 17

Among the cationic quinone chromophores A and/or A′, those mentioned in the abovementioned Colour Index International are suitable for use, and among those, mention may be made, inter alia, of the radicals derived from the following dyes:

-   -   Basic Blue 22     -   Basic Blue 99

Among the cationic azine chromophores A and/or A′, those listed in the Colour Index International are suitable for use, and among those, for example the radicals derived from the following dyes:

-   -   Basic Blue 17     -   Basic Red 2.

Among the cationic triarylmethane chromophores A and/or A′ that may be used according to the invention, mention may be made, besides those listed in the Colour Index, of the radicals derived from the following dyes:

-   -   Basic Green 1     -   Basic Violet 3     -   Basic Violet 14     -   Basic Blue 7     -   Basic Blue 26.

Mention may also be made of the cationic chromophores derived from the dyes described in documents U.S. Pat. No. 5,888,252, EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954. Mention may also be made of those listed in the encyclopaedia “The chemistry of synthetic dye” by K. Venkataraman, 1952, Academic press vol. 1 to 7, in Kirk Othmer's encyclopaedia “Chemical technology”, in the chapter “Dyes and dye intermediates”, 1993, Wiley and sons, and in various chapters of “Ullmann's Encyclopedia of Industrial Chemistry” 7th edition, Wiley and sons.

Preferably, the chromophores A and/or A′ are chosen from those derived from dyes of azo and hydrazono type.

According to one particular embodiment, the cationic radicals A and/or A′ in formula (I) comprise at least one cationic azo chromophore derived from a dye described in EP 850 636, FR 2 788 433, EP 920 856, WO 99/48465, FR 2 757 385, EP 85/0637, EP 91/8053, WO 97/44004, FR 2 570 946, FR 2 285 851, DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1 540 423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388, DE 4 137 005, WO 01/66646, U.S. Pat. No. 5,708,151, WO 95/01772, WO 515 144, GB 1 195 386, U.S. Pat. No. 3,524,842, U.S. Pat. No. 5,879,413, EP 1 062 940, EP 1 133 976, GB 738 585, DE 2 527 638, FR 2 275 462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chim. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211; Rev. Roum. Chim. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chim. Ind. (Milan) (1974), 56(9), 600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; MRL Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72.

According to one variant, A and/or A′ of formula (I) contain at least one cationic radical borne by, or included in, at least one of the chromophores.

Preferably, the cationic radical is a quaternary ammonium; more preferentially, the cationic charge is endocyclic.

These cationic radicals are, for example, a cationic radical:

-   -   bearing an exocyclic (di/tri)(C₁-C₈)alkylammonium charge, or     -   bearing an endocyclic charge, such as the following cationic         heteroaryl groups: acridinium, benzimidazolium,         benzobistriazolium, benzopyrazolium, benzopyridazinium,         benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium,         bipyridinium, bis-tetrazolium, dihydrothiazolium,         imidazopyridinium, imidazolium, indolium, isoquinolium,         naphthoimidazolium, naphthoxazolium, naphthopyrazolium,         oxadiazolium, oxazolium, oxazolopyridinium, oxonium,         phenazinium, phenoxazolium, pyrazinium, pyrazolium,         pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium,         pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium,         thiazolopyridinium, thiazoylimidazolium, thiopyrylium,         triazolium or xanthylium.

Mention may be made of the hydrazono cationic chromophores of formulae (II) and (III′), and the azo cationic chromophores (IV), (IV′), (V) and (V′) below:

(*)-Het⁺-C(R^(a))═N—N(R^(b))—Ar,Q⁻  (II)

Q⁻,Het⁺-C(R^(a))═N—N(R^(b))—Ar′—(*),  (II′)

(*)-Het⁺-N(R^(a))—N═C(R^(b))—Ar,Q⁻  (III)

Q⁻,Het⁺-N(R^(a))—N═C(R^(b))—Ar′—(*),  (III′)

(*)-Het⁺-N═N—Ar,Q⁻  (IV)

Q⁻,Het⁺-N═N—Ar′—(*),  (IV′)

(*)—Ar⁺—N═N—Ar″,Q⁻  (V)

Ar⁺—N═N—Ar″—(*)  (V′)

formulae (II) to (V′) with:

-   -   Het⁺ representing a cationic heteroaryl radical, preferentially         bearing an endocyclic cationic charge, such as imidazolium,         indolium or pyridinium, optionally substituted, preferentially         with one or more (C₁-C₈) alkyl groups such as methyl;     -   Ar⁺ represents an aralkyl radical, such as phenyl or naphthyl,         bearing an exocyclic cationic charge, particularly         tri(C₁-C₈)alkylammonium such as trimethylammonium;     -   Ar represents an aryl group, especially phenyl, optionally         substituted, preferentially with one or more electron-donating         groups such as i) optionally substituted (C₁-C₈)alkyl, ii)         optionally substituted (C₁-C₈)alkoxy, iii)         (di)(C₁-C₈)(alkyl)amino optionally substituted on the alkyl         group(s) with a hydroxyl group, iv) aryl(C₁-C₈)alkylamino, v)         optionally substituted N—(C₁-C₈)alkyl-N-aryl(C₁-C₈)alkylamino or         alternatively Ar represents a julolidine group;     -   Ar′ is an optionally substituted divalent (hetero)alkylene group         such as phenylene, particularly para-phenylene, or naphthalene,         which are optionally substituted, preferentially with one or         more groups (C₁-C₈)alkyl, hydroxyl or (C₁-C₈)alkoxy;     -   Ar″ is an optionally substituted (hetero)aryl group such as         phenyl or pyrazolyl, which are optionally substituted,         preferentially with one or more groups (C₁-C₈)alkyl, hydroxyl,         (di)(C₁-C₈)(alkyl)amino, (C₁-C₈)alkoxy or phenyl;     -   R^(a) and R^(b), which may be identical or different, represent         a hydrogen atom or a group (C₁-C₈)alkyl, which is optionally         substituted, preferentially with a hydroxyl group; or         alternatively the substituent R^(a) with a substituent of Het⁺         and/or R^(b) with a substituent of Ar form, together with the         atoms that bear them, a (hetero)cycloalkyl; particularly, R^(a)         and R^(b) represent a hydrogen atom or a group (C₁-C₄)alkyl,         which is optionally substituted with a hydroxyl group;     -   Q⁻ represents an organic or mineral anionic counterion such as a         halide or an alkyl sulfate;     -   (*) represents the part of the chromophore linked to the rest of         the molecule of formula (I).

In particular, mention may be made of the azo and hydrazono chromophores bearing an endocyclic cationic charge of formulae (II) to (IV′) as defined previously. More particularly those of formulae (II) to (IV′) derived from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferentially the following chromophores:

formulae (III-1) and (IV-1) with:

-   -   R¹ representing a group (C₁-C₄)alkyl such as methyl;     -   R² and R³, which may be identical or different, representing a         hydrogen atom or a group (C₁-C₄)alkyl such as methyl; and     -   R⁴ representing a hydrogen atom or an electron-donating group         such as optionally substituted (C₁-C₈)alkyl, optionally         substituted (C₁-C₈)alkoxy, or (di)(C₁-C₈)(alkyl)amino optionally         substituted on the alkyl group(s) with a hydroxyl group;         particularly, R⁴ is a hydrogen atom,     -   Z represents a group CH or a nitrogen atom, preferentially CH,     -   Q⁻ is as defined previously;         it being understood that the chromophore (II-1) or (IV-1) is         linked to the rest of the molecule of formula (I) by R², R¹ or         R⁴ in which case one of the hydrogen atoms of R², R¹ or R⁴ is         substituted with X or X′ if p=1 or p′=1 or alternatively with         C_(sat) or C_(sat′) if p=0 or p′=0.

Particularly, the chromophores (1′-1) and (IV-1) are derived from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof:

with Q′ being an anionic counterion as defined previously, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesityl.

According to one particular embodiment of the invention, the dyes of formula (I) are fluorescent, i.e. they contain at least one fluorescent chromophore as defined previously.

As fluorescent chromophores A and/or A′ that are useful in the present invention, mention may be made of radicals derived from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}bores (BODIPY®), diketopyrrolopyrroles, fluorindines, (poly)methines (especially cyanins and styryls/hemicyanins), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes and xanthenes.

Mention may also be made of the fluorescent dyes A and/or A′ described in documents EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144, EP 714 954 and those listed in the encyclopaedia The chemistry of synthetic dyes by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in Kirk Othmer's encyclopaedia Chemical Technology, in the chapter “Dyes and dye Intermediates”, 1993, Wiley and Sons, and in various chapters of Ullmann's Encyclopedia of Industrial Chemistry 7th edition, Wiley and Sons, and in The Handbook—A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes/Invitrogen—Oregon 2005 circulated on the Internet or in the preceding printed editions.

According to one preferred variant of the invention, the fluorescent chromophore A and/or A′ is cationic and comprises at least one quaternary ammonium radical such as those derived from the polymethine dyes of formulae (VI) and (VI′) below:

W⁺—[C(R^(c))═C(R^(d))]_(m′)—Ar′—(*)Q-  (VI)

Ar—[C(R^(d))═C(R^(c))]_(m′)—W′⁺—(*)Q⁻  (VI′)

formula (VI) or (VI′) with:

-   -   W⁺ representing a cationic heterocyclic or heteroaryl group,         particularly comprising a quaternary ammonium optionally         substituted with one or more groups (C₁-C₈)alkyl optionally         substituted especially with one or more hydroxyl groups;     -   representing a divalent heterocyclic or heteroaryl radical as         defined for W⁺;     -   Ar representing an aryl group such as phenyl or naphthyl,         optionally substituted preferentially with i) one or more         halogen atoms such as chlorine or fluorine; ii) one or more         groups (C₁-C₈)alkyl, preferably of C₁-C₄ such as methyl; iii)         one or more hydroxyl groups; iv) one or more (C₁-C₈)alkoxy         groups such as methoxy; v) one or more hydroxy(C₁-C₈)alkyl         groups such as hydroxyethyl, vi) one or more amino groups or         (di)(C₁-C₈)alkylamino, preferably with the C₁-C₄ alkyl part         optionally substituted with one or more hydroxyl groups, such as         (di)hydroxyethylamino, vii) with one or more acylamino         groups; viii) one or more heterocycloalkyl groups such as         piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as         pyrrolidinyl, pyridyl and imidazolinyl;     -   Ar′ is a divalent aryl radical as defined for Ar;     -   m′ represents an integer between 1 and 4 inclusive, and in         particular m is 1 or 2; more preferentially 1;     -   R^(c) and R^(d), which may be identical or different, represent         a hydrogen atom or an optionally substituted group (C₁-C₈)alkyl,         preferentially of C₁-C₄, or alternatively R^(c) contiguous with         W⁺ or W′⁺ and/or R^(d) contiguous with Ar or Ar′ form, with the         atoms that bear them, a (hetero)cycloalkyl, particularly R^(c)         is contiguous with W⁺ or W′⁺ and forms a (hetero)cycloalkyl such         as cyclohexyl;     -   Q⁻ is an organic or mineral anionic counterion as defined         previously;     -   (*) represents the part of the chromophore linked to the rest of         the molecule of formula (I).

According to another variant, the disulfide, thiol or protected-thiol dye is a quaternized or quaternizable fluorescent dye such that, in formula (I) with p and p′ equal to 1 and A and/or A′ representing a naphthalimidyl radical optionally bearing an exocyclic cationic charge of formula (VII) or (VII′):

in which formulae (VII) and (VII′):

-   -   R^(e), R^(f), R^(g) and R^(h), which may be identical or         different, representing a hydrogen atom or a (C₁-C₆) alkyl group         which is optionally substituted, preferentially with a         di(C₁-C₆)alkylamino or tri(C₁-C₆)alkyl ammonium group such as         trimethylammonium;     -   representing the bond the links the naphthalimidyl radical to         the rest of the molecule via X or X′, if p=1 or p′=1 or         alternatively via Csat or Csat′ if p=0 or p′=0.

According to one embodiment of the invention, p=1, z=f=0, t=1 and T represents —N(R)—, preferably in the para position on Ar relative to the olefin function —C(R^(c))═C(R^(d))—.

Particularly, in one variant, p=1, z=t′=0, t=1 and T represents —N(R)—, preferably in the para position on Ar relative to the styryl function —C(Rc)═C(Rd)— and T′ represents a group —N(R)— or —N+(R)(R^(o))— or an imidazolium.

Preferably, W⁺ or W′⁺ is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium optionally substituted with one or more identical or different C₁-C₄ alkyl radicals.

According to one particularly preferred embodiment of the invention, A and/or A′ represent the chromophore (VI′) as defined previously with m′=1, Ar representing a phenyl group substituted para to the styryl group —C(R^(d))═C(R^(c))— with a group (di)(hydroxy)(C₁-C₆)(alkyl)amino such as dihydroxy(C₁-C₄)alkylamino, and representing an imidazolium or pyridinium group, preferentially ortho- or para-pyridinium.

As examples of dyes of the invention, mention may be made of the disulfide dyes chosen from formulae (VIII) to (XIV) and the thiol or protected-thiol dyes chosen from formulae (VIII′) to (XIV′) below:

in which formulae (VIII) to (XIV) and (VIII′) to (XIV′):

-   -   G and G′, which may be identical or different, represent a group         —NR_(c)R_(d), —NR′_(c)R′_(d) or C₁-C₆ alkoxy which is optionally         substituted, preferentially unsubstituted; preferentially, G and         G′ represent a group —NR_(c)R_(d) or —NR′_(c)R′_(d),         respectively;     -   R¹, R², R³ and R⁴, which may be identical or different,         represent a hydrogen atom or a C₁-C₆ alkyl group; preferentially         a hydrogen atom;     -   R_(a) and R′_(a), which may be identical or different, represent         an aryl(C₁-C₄)alkyl group or a C₁-C₆ alkyl group optionally         substituted with a hydroxyl or amino, C₁-C₄ alkylamino or C₁-C₄         dialkyl amino group, the said alkyl radicals possibly forming,         with the nitrogen atom that bears them, a 5- to 7-membered         heterocycle, optionally comprising another nitrogen or         non-nitrogen heteroatom; preferentially, R_(a) and R′_(a)         represent a C₁-C₃ alkyl group optionally substituted with a         hydroxyl group, or a benzyl group;     -   R_(b) and R′_(b), which may be identical or different, represent         a hydrogen atom, an aryl(C₁-C₄)alkyl group or a C₁-C₆ alkyl         group that is optionally substituted; preferentially, R_(b) and         R′_(b) represent a hydrogen atom or a C₁-C₃ alkyl or benzyl         group;     -   R_(c), R′_(c), R_(d) and R′_(d), which may be identical or         different, represent a hydrogen atom, an aryl(C₁-C₄)alkyl or         C₁-C₆ alkoxy group or a C₁-C₆ alkyl group that is optionally         substituted; R_(c), R′_(c), R_(d) and R′_(d) preferentially         represent a hydrogen atom, a hydroxyl, C₁-C₃ alkoxy, amino or         C₁-C₃ (di)alkylamino group, or a C₁-C₃ alkyl group that is         optionally substituted with i) a hydroxyl group, ii) amino, iii)         C₁-C₃ (di)alkylamino, or iv) quaternary ammonium         (R″)(R′″)(R″″)N⁺—;     -   or alternatively two adjacent radicals R_(c) and R_(d), R′_(c)         and R′_(d) borne by the same nitrogen atom together form a         heterocyclic or heteroaryl group; preferentially, the         heterocycle or heteroaryl is monocyclic and 5- to 7-membered;         more preferentially, the groups are chosen from imidazolyl and         pyrrolidinyl;     -   R_(e) and R′_(e), which may be identical or different, represent         a linear or branched C₁-C₆ alkylene or C₂-C₆ alkenylene         hydrocarbon-based chain;     -   R_(f) and R′_(f), which may be identical or different, represent         a group di(C₁-C₄)alkylamino, (R″)(R′″)N— or a quaternary         ammonium group (R″)(R′″)(R″″)N⁺— in which R″, R′″ and R″″, which         may be identical or different, represent a hydrogen atom or a         C₁-C₄ alkyl group or alternatively (R″)(R′″)(R″″)N⁺— represent         an optionally substituted cationic heteroaryl group,         preferentially an imidazolinium group optionally substituted         with a C₁-C₃ alkyl group;     -   R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h), R″_(h), and         R′″_(h), which may be identical or different, represent a         hydrogen atom, a halogen atom, an amino, C₁-C₄ alkylamino, C₁-C₄         dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl         group, an acylamino, C₁-C₄ alkoxy, (poly)hydroxy(C₂-C₄)alkoxy,         alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical,         an acylamino, carbamoyl or alkylsulfonylamino radical, an         aminosulfonyl radical, or a C₁-C₁₆ alkyl radical optionally         substituted with a group chosen from C₁-C₁₂ alkoxy, hydroxyl,         cyano, carboxyl, amino, C₁-C₄ alkylamino and C₁-C₄ dialkylamino,         or alternatively two alkyl radicals borne by the nitrogen atom         of the amino group form a 5- to 7-membered heterocycle         optionally comprising another nitrogen or non-nitrogen         heteroatom; preferentially, R_(g), R′_(g), R″_(h), R′ ″_(g),         R_(h), R′_(h), R″_(h), and R′″_(h) represent a hydrogen or         halogen atom or a C₁-C₃ alkyl group;     -   or alternatively two groups R_(g) and R′_(g), R″_(g) and         R′″_(g), R_(h), and R′_(h); R″_(h) and R′″_(h) borne by two         adjacent carbon atoms together form a benzo or indeno ring, a         fused heterocycloalkyl or fused heteroaryl group; the benzo,         indeno, heterocycloalkyl or heteroaryl ring being optionally         substituted with a halogen atom, an amino, C₁-C₄ alkylamino,         C₁-C₄ dialkylamino, nitro, cyano, carboxyl, hydroxyl or         trifluoromethyl group, an acylamino, C₁-C₄ alkoxy,         (poly)hydroxy(C₂-C₄)alkoxy, alkylcarbonyloxy, alkoxycarbonyl or         alkylcarbonylamino radical, an acylamino, carbamoyl or         alkylsulfonylamino radical, an aminosulfonyl radical, or a         C₁-C₁₆ alkyl radical optionally substituted with: a group chosen         from C₁-C₁₂ alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄         alkylamino, C₁-C₄ dialkylamino, or alternatively two alkyl         radicals borne by the nitrogen atom of the amino group form a 5-         to 7-membered heterocycle optionally comprising another nitrogen         or non-nitrogen heteroatom; preferentially, R_(g) and R′_(g),         R″_(g) and R′″_(g) together form a benzo group;     -   or alternatively two groups R_(i) and R_(g), R′″_(i) and         R′″_(g), R′_(i) and R′_(h); and/or R″_(i) and R″_(h) together         form a fused (hetero)cycloalkyl, preferentially cycloalkyl such         as cyclohexyl;     -   or alternatively when G represents —NR_(c)R_(d) and G′         represents —NR′_(c)R′_(d), two groups R_(c) and R′_(g); and         R″_(g); R_(d) and R_(g), R′_(d) and R′″_(g) together form a         saturated heteroaryl or heterocycle, optionally substituted with         one or more groups (C₁-C₆)alkyl, preferentially a 5- to         7-membered heterocycle containing one or two heteroatoms chosen         from nitrogen and oxygen; more preferentially the heterocycle is         chosen from morpholinyl, piperazinyl, piperidyl and pyrrolidinyl         groups;     -   R_(i), R′_(i), R″_(i), and R′″_(i), which may be identical or         different, represent a hydrogen atom or a C₁-C₄ alkyl group;     -   R₁, R₂, R₃, R₄, R′₁, R′₂, R′₃, and R′₄, which may be identical         or different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₁₂         alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino or         C₁-C₄ dialkylamino group, the said alkyl radicals possibly         forming with the nitrogen that bears them a 5- to 7-membered         heterocycle optionally comprising another nitrogen or         non-nitrogen heteroatom; preferentially, R₁, R₂, R₃, R₄, R′₁,         R′₂, R′₃, and R′₄ are hydrogen atoms or an amino group; more         preferentially, R₁, R₂, R₃, R₄, R′₁, R′₂, R′₃, and R′₄ represent         a hydrogen atom;     -   T_(a), T_(b), which may be identical or different, represent i)         either a covalent bond, ii) or one or more radicals or         combinations thereof chosen from —SO₂—, —O—, —S—, —N(R)—,         —N⁺(R)(R^(o)—, —CO—, with R, R^(o), which may be identical or         different, representing a hydrogen atom, a C₁-C₄ alkyl or C₁-C₄         hydroxyalkyl radical; or an aryl(C₁-C₄)alkyl, preferentially,         T_(a) is identical to T_(b) and represent a covalent bond or a         group chosen from —N(R)—, —C(O)—N(R)—, —N(R)—C(O)—, —O—C(O)—,         —C(O)—O— and —N⁺(R)(R^(o)—, with R, R^(o), which may be         identical or different, representing a hydrogen atom or a C₁-C₄         alkyl group; more preferentially, T_(a) and T_(b) represent a         bond; iii) or a cationic or non-cationic, preferentially         monocyclic, preferentially identical heterocycloalkyl or         heteroaryl radical, preferentially containing two heteroatoms         (more preferentially two nitrogen atoms) and preferentially         being 5- to 7-membered, such as imidazolium;

identical or different, represent an optionally substituted heterocyclic group; preferentially, the heterocycles are identical, monocyclic, saturated and 5- to 8-membered and comprise in total two nitrogen atoms;

represent an aryl or heteroaryl group fused to the imidazolium or phenyl ring; or alternatively is absent from the imidazolium or phenyl ring; preferentially, when the ring is present, the ring is a benzo;

-   -   m, m′, n and n′, which may be identical or different, represent         an integer between 0 and 6 inclusive, with m+n and m′+n′, which         may be identical or different, represents an integer between 1         and 10 inclusive; preferentially, m+n=m′+n′=an integer between 2         and 4 inclusive; more preferentially, m+n=m′+n′=an integer equal         to 2;     -   Y is as defined previously; in particular, Y represents a         hydrogen atom or a protecting group such as:         -   (C₁-C₄)alkylcarbonyl, for instance methylcarbonyl or             ethylcarbonyl;         -   arylcarbonyl, for instance phenylcarbonyl;         -   (C₁-C₄)alkoxycarbonyl;         -   aryloxycarbonyl;         -   aryl(C₁-C₄)alkoxycarbonyl;         -   (di)(C₁-C₄)(alkyl)aminocarbonyl, for instance             dimethylaminocarbonyl;         -   (C₁-C₄)(alkyl)arylaminocarbonyl;         -   optionally substituted aryl such as phenyl;         -   5- or 6-membered monocyclic heteroaryl such as imidazolyl or             pyridyl;         -   cationic 5- or 6-membered monocyclic heteroaryl such as             pyrylium, pyridinium, pyrimidinium, pyrazinium,             pyridazinium, triazinium, imidazolium; these groups being             optionally substituted with one or more identical or             different (C₁-C₄)alkyl groups such as methyl;         -   cationic 8- to 11-membered bicyclic heteroaryl such as             benzimidazolium or benzoxazolium; these groups being             optionally substituted with one or more identical or             different (C₁-C₄)alkyl groups such as methyl;         -   cationic heterocycle having the following formula:

-   -   -   —C(NH₂)═N⁺H₂; An′″⁻; with An′″⁻ being an anionic counterion             as defined previously;         -   —C(NH₂)═NH;         -   SO₃ ⁻, M⁺ with M⁺ representing an alkali metal such as             sodium or potassium. and

    -   M′ representing an anionic counterion, derived from a salt of an         organic or mineral acid, or from an organic or mineral base that         ensures the electrical neutrality of the molecule.

In particular, the dyes of formula (I) are chosen from dyes with a naphthalimidyl disulfide, thiol or protected-thiol chromophore, chosen from formulae (XIII), (XIII′), (XIV) and (XIV′) as defined previously.

According to one preferred mode of the invention, the dyes of formula (I) are chosen from disulfide, thiol or protected-thiol dyes chosen from formulae (XV) to (XV′) below:

the organic or mineral acid salts, optical isomers, geometrical isomers, and solvates such as hydrates thereof; in which formulae (XV) and (XV′):

-   -   R and R′″, which may be identical or different, represent a         hydroxyl group, an amino group (NR_(a)R_(b)) or an ammonium         group (N⁺R_(a)R_(b)R_(c)), An⁻; preferentially hydroxyl; with         R_(a), R_(b) and R_(c), which may be identical or different,         representing a hydrogen atom or a (C₁-C₄)alkyl group;     -   or alternatively two alkyl groups R_(a) and R_(b) of the amino         or ammonium group form a 5- to 7-membered heterocycle optionally         comprising another nitrogen or non-nitrogen heteroatom, such as         morpholinyl, piperazinyl, piperidyl, pyrrolyl, morpholinium,         piperazinium, piperidinium or pyrrolinium, and An⁻ representing         an anionic counterion;     -   R′ and R″, which may be identical or different, represent a         hydrogen atom or a group as defined for R and R′″, respectively;         —R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h), R″_(h) and         R′″_(h), which may be identical or different, represent a         hydrogen or halogen atom, an amino, (di)(C₁-C₄)alkylamino,         cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C₁-C₄         alkoxy, C₂-C₄ (poly)hydroxyalkoxy, (C₁-C₄)alkylcarbonyloxy,         (C₁-C₄)alkoxycarbonyl, (C₁-C₄)alkylcarbonylamino, acylamino,         carbamoyl or (C₁-C₄)alkylsulfonylamino group, an aminosulfonyl         radical or a radical (C₁-C₁₆)alkyl optionally substituted with a         group chosen from (C₁-C₁₂)alkoxy, hydroxyl, cyano, carboxyl and         (di)(C₁-C₄)alkylamino, or alternatively the two alkyl radicals         borne by the nitrogen atom of the amino group form a 5- to         7-membered heterocycle optionally comprising another nitrogen or         non-nitrogen heteroatom; in particular, R_(g), R′_(g), R″_(g),         R′″_(g), R_(h), R′_(h), R″_(h) and R′″_(h) represent a hydrogen         atom or a (C₁-C₄) alkyl group;     -   R′i, R″i, R′″i and R″″i, which may be identical or different,         represent a hydrogen atom or a (C₁-C₄)alkyl group; in particular         R′_(i), R″_(i), R′″_(i), and R″″_(i) represent a hydrogen atom;     -   m, m′, which may be identical or different, represent an integer         between 1 and 10 inclusive; in particular an integer between 2         and 4 inclusive; preferentially, m and m′ are equal to 2;     -   p, p′, q and q′, which may be identical or different, represent         an integer between 1 and 6 inclusive;     -   M′ representing an anionic counterion; and     -   Y is as defined previously;     -   it being understood that when the compound of formula (XV) or         (XV′) contains other cationic parts, it is combined with one or         more anionic counterions that afford formula (XV) or (XV′)         electrical neutrality.

According to one particular mode of the invention, the dyes of the invention belong to formula (XVa) or (XV′a) which bear an ethylene group connecting the pyridinium part to the phenyl ortho or para to the pyridinium, i.e. 2-4′, 4-2′, 4-4′:

with R, R′, R″, R′″, R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h), R″_(h), R′″_(h), R′_(i), R″_(i), R′″_(i), R″″_(i), m, m′, p, p′, q, q′, Y and M′ as defined previously in formulae (XV) and (XV′). In particular, R_(h) and R″_(h) are ortho to the pyridinium group and R′_(h) and R″_(h) represent a hydrogen atom. Another aspect of the invention concerns the dyes of formula (XVa) or (XV′a) bearing groups R_(g), R″_(g) in position 3′ and R′_(g)/R″_(g) which represent a hydrogen atom.

Advantageously, the dyes of formulae (XVa) and (XV′a) bear their ethylene group para to the phenyl bearing the amino group: R′(CH₂)_(p)—N—(CH₂)_(q)—R and/or R″(CH₂)_(p′)—N—(CH₂)_(q′)—R′″, i.e. in position 4′, preferentially bear an ethylene or styryl group linking the pyridinium part to the phenyl ortho to the pyridinium, i.e. 2-4′.

According to another particular mode of the invention, the dyes of the invention belong to formula (XVI) or (XVI′):

in which formula (XVI) or (XVI′):

-   -   R₁ represents a C₁-C₆ alkyl group substituted with one or more         hydroxyl groups or —C(O)OR′ with R′ representing a hydrogen         atom, a C₁-C₄ alkyl group or a group —C(O)—O⁻ and, in the latter         case, an anionic counterion An⁻ is absent; in particular R₁         represents a C₁-C₆ alkyl group substituted with one or more         hydroxyl groups and more specifically with only one hydroxyl         group;     -   R₂ represents a C₁-C₆ alkyl group optionally substituted with         one or more hydroxyl groups;     -   or alternatively the groups R₁ and R₂ form, together with the         nitrogen atom that bears them, a saturated heterocyclic radical         substituted with at least one hydroxyl,         (poly)hydroxy(C₁-C₄)alkyl and/or —C(O)OR′ group with R′         representing a hydrogen atom, a C₁-C₄ alkyl group or a group         —C(O)—O⁻ and, in the latter case, an anionic counterion An⁻ is         absent; such as pyrrolidinyl and piperidyl;     -   R₃ represents a hydrogen atom or a group —C(O)OR″ with R″         representing a hydrogen atom, an alkali metal or a C₁-C₆ alkyl         group or alternatively R₃ represents a group —C(O)—O⁻ and, in         the latter case, an anionic counterion An⁻ is absent;     -   Z represents a divalent amido group —C(O)—N(R)—, —N(R)—C(O)—, or         a divalent C₁-C₁₀ alkylene group interrupted with an amido group         —C(O)—N(R)—, —N(R)—C(O)— such as         —(CH₂)_(n′)—C(O)—N(R)—(CH₂)_(p)—,         —(CH₂)_(n″)—N(R)—C(O)—(CH₂)_(p)—, with n′ representing an         integer between 0 and 3 inclusive; preferentially, n′ is equal         to 0, 2, 3; p representing an integer between 0 and 4 inclusive,         n″ representing an integer between 0 and 3 inclusive and         especially n′=n″=p=0 and R representing a hydrogen atom or a         C₁-C₆ alkyl group;     -   An⁻ represents an anionic counterion;     -   Y is as defined previously;         it being understood that when the compound of formula (XVI) or         (XVI′) contains other cationic parts, it is combined with one or         more anionic counterions that afford formula (XVI) or (XVI′)         electrical neutrality.

According to another particular mode of the invention, the dyes of the invention belong to formula (XVIa) or (XVI′a):

in which formulae (Ia) and (Ib):

-   -   R′₁ represents a C₁-C₄ alkyl group substituted with one or more         hydroxyl groups, particularly with only one hydroxyl group, or         —C(O)OR′ with R′ representing a hydrogen atom, a C₁-C₄ alkyl         group or a group —C(O)—O⁻ and, in the latter case, an anionic         counterion An⁻ is absent; preferentially, R′₁ represents a C₁-C₄         alkyl group substituted with a hydroxyl group;     -   R′₂ represents a C₁-C₄ alkyl group optionally substituted with         one or more hydroxyl groups, particularly with only one hydroxyl         group; more particularly, R′₁ and R′₂ are identical;     -   An⁻ represents an anionic counterion as defined previously;     -   B represents a divalent amido group —C(O)—N(R)—, —N(R)—C(O)—,         with R representing a hydrogen atom or a group (C₁-C₆)alkyl;         preferentially, R═H;     -   n and m, which may be identical or different, represent an         integer between 1 and 4 inclusive; preferentially, n is equal to         3 and m is equal to 2;     -   Y is as defined previously;         it being understood that the bond between the pyridinium ring         and the double bond of the ethylene or styryl group is located         in position 2 or 4 of the pyridinium, preferentially at 4.

As examples of disulfide, thiol and protected-thiol direct dyes of formula (I) of the invention, mention may be made of those having the following chemical structures:

with An⁻ and M', which may be identical or different, preferentially identical, representing anionic counterions. More particularly, the anionic counterion is chosen from halides such as chloride, alkyl sulfates such as methyl sulfate, mesylate and ½(O=)₂SO²⁻ or ½ SO₄ ²⁻.

More preferentially, the dyes i) as defined previously are chosen from compounds 44, 49, 49a and 55, especially 44, 49 and 55.

According to one particularly advantageous embodiment of the invention, the dye 0 is a dye comprising a “permanent” cationic charge, i.e. containing in its structure at least one quaternized nitrogen atom (ammonium) or quaternized phosphorus atom (phosphonium); preferentially quaternized nitrogen.

The composition according to the invention contains, in a cosmetic medium, an amount of dyes bearing a disulfide, thiol or protected-thiol function as defined previously, especially of formula (I) as defined previously, generally inclusively between 0.001% and 30% relative to the total weight of the composition.

Preferably, the amount of dyes bearing a disulfide, thiol or protected-thiol function as defined previously, especially of formula (I), is inclusively between 0.01% and 5% by weight relative to the total weight of the composition. By way of example, the dye(s) are in an amount of between 0.01% and 2%.

i). 5). The Cosmetically Acceptable Organic or Mineral Acid Salt and Counterion of the Dyes of the Invention

They are chosen from the “organic or mineral acid salt” and “anionic counterion” as defined previously.

Moreover, the addition salts that may be used in the context of the invention may be chosen from addition salts with a cosmetically acceptable base such as basifying agents as defined below, for instance alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, aqueous ammonia, amines or alkanolamines.

ii) At Least One Fatty Alcohol;

The composition of the invention comprises one or more sparingly ethoxylated or non-ethoxylated fatty alcohols.

The sparingly ethoxylated fatty alcohols that are suitable for performing the invention are chosen more particularly from saturated or unsaturated alcohols containing from 8 to 40 carbon atoms and preferably from 12 to 22 carbon atoms, and from 1 to 6 and preferably from 1 to 3 ethylene oxide units.

If they are unsaturated, these compounds may comprise one to three conjugated or non-conjugated carbon-carbon double bonds.

The sparingly ethoxylated fatty alcohol(s) preferably have the following formula:

R^(a)—[O—CH₂—CH₂]_(n)—OH

with

-   -   R^(a) representing a linear or branched C₈-C₄₀ alkyl or linear         or branched C₈-C₄₀ and preferably C₈-C₃₀ alkenyl group,         optionally substituted with one or more hydroxyl groups, and     -   n is an integer between 1 and 6 inclusive, preferentially         between 1 and 3 and more particularly between 1 and 2 inclusive.

Among the sparingly ethoxylated fatty alcohols, mention may be made more particularly of lauryl alcohol containing 2 OE, lauryl alcohol containing 3 OE, decyl alcohol containing 3 OE, decyl alcohol containing 5 OE, stearyl alcohol containing 2 OE, stearyl alcohol containing 3 OE, stearyl alcohol containing 4 OE, stearyl alcohol containing 5 OE, cetyl alcohol containing 2 OE, cetyl alcohol containing 3 OE, cetyl alcohol containing 4 OE and cetyl alcohol containing 5 OE, and mixtures thereof, such as cetearyl alcohol containing 3 OE, cetearyl alcohol containing 4 OE and cetearyl alcohol containing 5 OE.

Advantageously, the ethoxylated fatty alcohol is solid or pasty at a temperature of 25° C. For the purposes of the present invention, the term “fatty alcohol that is solid or pasty at 25° C.” means a fatty alcohol that has a viscosity, measured with a rheometer (for example an R⁶⁰⁰ rheometer) at a shear rate of 1 s⁻¹, of greater than or equal to 1 Pa·s.

Preferably, the sparingly ethoxylated fatty alcohols are saturated, linear sparingly ethoxylated fatty alcohols.

The fatty alcohols of the invention may be “non-ethoxylated”, i.e. they do not comprise in their structure any ethylene oxide groups —CH₂—CH₂—O—.

In this case, the fatty alcohol has the structure R—OH, in which R denotes a saturated or unsaturated, linear or branched radical comprising from 8 to 40 and preferably from 8 to 30 carbon atoms; R may be substituted with one or more hydroxyl groups and preferably with one or two hydroxyl groups.

Examples that may be mentioned include lauryl alcohol, cetyl alcohol, stearyl alcohol, oeyl alcohol, behenyl alcohol, linoleyl alcohol, undecylenyl alcohol, palmitoleyl alcohol, arachidonyl alcohol and erucyl alcohol, and mixtures thereof.

The fatty alcohol may represent a mixture of fatty alcohols, which means that several species of fatty alcohol may coexist, in the form of a mixture, in a commercial product.

Advantageously, the fatty alcohol is solid or pasty at a temperature of 25° C. For the purposes of the present invention, the term “fatty alcohol that is solid or pasty at 25° C.” means a fatty alcohol that has a viscosity, measured with a rheometer (for example an R600 rheometer) at a shear rate of 1 s⁻¹, of greater than or equal to 1 Pa·s.

Preferentially, the fatty alcohol used in the cosmetic composition according to the invention is chosen from myristyl alcohol, cetyl alcohol, stearyl alcohol and palmityl alcohol, and mixtures thereof, such as cetylstearyl alcohol.

Even more preferentially, the fatty alcohols used in the cosmetic composition according to the invention are stearyl alcohol or cetyl alcohol and mixtures thereof, such as cetylstearyl alcohol especially at 50/50.

Preferably, the non-ethoxylated fatty alcohols are saturated, linear non-ethoxylated fatty alcohols.

Preferably, the sparingly ethoxylated or non-ethoxylated fatty alcohol according to the invention is a non-ethoxylated fatty alcohol.

The sparingly ethoxylated or non-ethoxylated fatty alcohol(s) used in the composition according to the present invention may be present in the composition in an amount ranging from 0.01% to 30%, preferably in an amount ranging from 0.1% to 20% and even more preferentially in an amount ranging from 0.5% to 10% by weight relative to the total weight of the composition.

iii) At Least One Cationic Surfactant;

The oxidizing composition comprises one or more cationic surfactants. Mention may be made, for example, of optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may especially be mentioned include:

a) those corresponding to the general formula (XVII) below:

in which formula (XVII) the groups R₈ to R₁₁, which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms or an aromatic group such as aryl or alkylaryl, at least one of the groups R₈ to R₁₁ comprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms. The aliphatic groups may comprise heteroatoms such as, in particular, oxygen, nitrogen, sulfur and halogens.

The aliphatic groups are chosen, for example, from C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, polyoxy(C₂-C₆)alkylene, C₁-C₃₀ alkylamide, (C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl, (C₁₂-C₂₂)alkylacetate, C₁-C₃₀ hydroxyalkyl, X⁻ is an anionic counterion chosen from halides, phosphates, acetates, lactates, (C₁-C₄)alkyl sulfates, and (C₁-C₄)alkyl- or (C₁-C₄)alkylarylsulfonates.

Among the quaternary ammonium salts of formula (XVII), preference is given firstly to tetraalkylammonium halides such as tetraalkylammonium chlorides, for instance tetraalkylammonium or alkyltrimethylammonium halides such as dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains from approximately 12 to 22 carbon atoms, in particular halides such as behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, alkoxy sulfates, especially distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium halide, particularly the chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name Ceraphyl® 70 by the company Van Dyk;

b) quaternary ammonium salts of imidazoline, for instance those of formula (XVIII) below:

in which formula (XVIII):

-   -   R₁₂ represents an alkenyl or alkyl group comprising from 8 to 30         carbon atoms, for example fatty acid derivatives of tallow;     -   R₁₃ represents a hydrogen atom, a C₁-C₄ alkyl group or an         alkenyl or alkyl group comprising from 8 to 30 carbon atoms;     -   R₁₄ represents a C₁-C₄ alkyl group;     -   R₁₅ represents a hydrogen atom or a C₁-C₄ alkyl group;     -   X⁻ represents an anionic counterion chosen in particular from         halides, phosphates, acetates, lactates, (C₁-C₄)alkyl sulfates,         (C₁-C₄)alkyl- or (C₁-C₄)alkylarylsulfonates.

R₁₂ and R₁₃ preferably denote a mixture of alkyl or alkenyl groups containing from 12 to 21 carbon atoms, derived for example from tallow fatty acids, R₁₄ preferably denotes a methyl group, and R₁₅ preferably denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;

c) quaternary diammonium or triammonium salts, particularly of formula (XIX) below:

in which formula (XIX):

-   -   R₁₆ denotes an alkyl group comprising from about 16 to 30 carbon         atoms, which is optionally hydroxylated and/or interrupted with         one or more oxygen atoms;     -   R₁₇ is chosen from hydrogen, an alkyl group comprising from 1 to         4 carbon atoms or a group —(CH₂)₃—N⁺(R_(16a))(R_(17a))(R_(18a));         R_(16a), R_(17a), R_(18a), R₁₈, R₁₉, R₂₀ and R₂₁, which may be         identical or different, are chosen from hydrogen and an alkyl         group comprising from 1 to 4 carbon atoms, and     -   X⁻ represents an anionic counterion chosen in particular from         halides, acetates, phosphates, nitrates, (C₁-C₄)alkyl sulfates,         (C₁-C₄)alkyl- or (C₁-C₄)alkylarylsulfonates, in particular         methyl sulfate and ethyl sulfate. Such compounds are, for         example, Finquat CT-P, available from the company Finetex         (Quaternium 89), and Finquat CT, available from the company         Finetex (Quaternium 75);

d) quaternary ammonium salts containing one or more ester functions, such as those of formula (XX) below:

in which formula (XX):

-   -   R₂₂ is chosen from C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl or         dihydroxyalkyl groups;     -   R₂₃ is chosen from:         -   the group

-   -   -   linear or branched, saturated or unsaturated C₁-C₂₂             hydrocarbon-based groups R₂₇,         -   a hydrogen atom;

    -   R₂₅ is chosen from:         -   the group

-   -   -   linear or branched, saturated or unsaturated C₁-C₆             hydrocarbon-based groups R₂₉,         -   a hydrogen atom;

    -   R₂₄, R₂₆ and R₂₈, which may be identical or different, are         chosen from linear or branched, saturated or unsaturated C₇-C₂₁         hydrocarbon-based groups;

    -   r, s and t, which may be identical or different, are integers         ranging from 2 to 6;

    -   r1 and t1, which may be identical or different, are equal to 0         or 1, with r2+r1=2r and t1+t2=2t,

    -   y is an integer ranging from 1 to 10;

    -   x and z, which may be identical or different, are integers         ranging from 0 to 10;

    -   X⁻ represents an organic or inorganic anionic counterion;         with the proviso that the sum x+y+z is from 1 to 15, that when x         is 0, then R₂₃ denotes R₂₇ and that when z is 0, then R₂₅         denotes R₂₉.

The alkyl groups R₂₂ may be linear or branched, and more particularly linear.

Preferably, R₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.

Advantageously, the sum x+y+z is from 1 to 10.

When R₂₃ is a hydrocarbon-based group R₂₇, it may be long and may contain from 12 to 22 carbon atoms, or may be short and may contain from 1 to 3 carbon atoms.

When R₂₅ is a hydrocarbon-based group R₂₉, it preferably contains 1 to 3 carbon atoms.

Advantageously, R₂₄, R₂₆ and R₂₈, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C₁₁-C₂₁ hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C₁₁-C₂₁ alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0 or 1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anionic counterion X⁻ is preferably a halide, preferably such as chloride, bromide or iodide, a (C₁-C₄)alkyl sulfate or a (C₁-C₄)alkyl- or (C¹-C₄)alkylaryl-sulfonate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion compatible with the ammonium containing an ester function.

The anionic counterion X⁻ is even more particularly chloride, methyl sulfate or ethyl sulfate.

Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (XX) in which:

-   -   R₂₂ denotes a methyl or ethyl group,     -   x and y are equal to 1,     -   z is equal to 0 or 1,     -   r, s and t are equal to 2,     -   R₂₃ is chosen from:         -   the group

-   -   -   methyl, ethyl or C₁₄-C₂₂ hydrocarbon-based groups,         -   a hydrogen atom,

    -   R₂₅ is chosen from:         -   the group

-   -   -   a hydrogen atom,

    -   R₂₄, R₂₆ and R₂₈, which may be identical or different, are         chosen from linear or branched, saturated or unsaturated C₁₃-C₁₇         hydrocarbon-based groups, and more particularly from linear or         branched, saturated or unsaturated C₁₃-C₁₇ alkyl and alkenyl         groups.

Advantageously, the hydrocarbon-based radicals are linear.

Among the quaternary ammonium salts containing one or more ester functions of formula (XX), examples that may be mentioned include salts, especially the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxy-ethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxy-ethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably methyl or ethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco. The composition according to the invention may contain, for example, a mixture of quaternary ammonium salts of mono-, di- and triesters with a weight majority of diester salts.

It is also possible to use the ammonium salts containing at least one ester function that are described in U.S. Pat. No. 4,874,554 and U.S. Pat. No. 4,137,180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.

Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Among the cationic surfactants that may be present in the composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.

According to the present invention, the cationic surfactant(s) are preferably present in the composition in an amount ranging from 0.01% to 40% by weight, preferably from 0.1% to 20% by weight and better still from 0.2% to 10% by weight, relative to the total weight of the composition.

iv) At Least One Alkaline Agent;

The composition according to the invention comprises one or more alkaline agents. This agent may be chosen from mineral or organic or hybrid alkaline agents, or mixtures thereof.

The mineral alkaline agent(s) are preferably chosen from aqueous ammonia, alkali carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.

According to one advantageous embodiment of the invention, the alkaline agent(s) are organic amines, i.e. they contain at least one substituted or unsubstituted amino group.

The organic alkaline agent(s) are preferentially chosen from organic amines with a pK_(b) at 25° C. of less than 12, preferably less than 10 and even more advantageously less than 6. It should be noted that it is the pK_(b) corresponding to the function of highest basicity.

Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.

The organic alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (XXI) below:

in which formula (XXI):

-   -   W is a divalent C₁-C₆ alkylene radical optionally substituted         with a hydroxyl group or a C₁-C₆ alkyl radical, and/or         optionally interrupted with one or more heteroatoms such as         oxygen or NR^(u);     -   R^(x), R^(y), R^(z) R^(t) and R^(u), which may be identical or         different, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆         hydroxyalkyl or C₁-C₆ aminoalkyl radical.

Examples of such amines that may be mentioned include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term “alkanolamine” means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C₁-C₈ alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different C₁-C₄ hydroxyalkyl radicals are in particular suitable for performing the invention.

Among compounds of this type, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol and tris(hydroxymethylamino)methane.

More particularly, the amino acids that may be used are of natural or synthetic origin, in their L, D or racemic form, and comprise at least one acid function chosen more particularly from carboxylic acid, sulfonic acid, phosphonic acid or phosphoric acid functions. The amino acids may be in neutral or ionic form.

As amino acids that may be used in the present invention, mention may be made especially of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.

Such basic amino acids are preferably chosen from those corresponding to formula (XXII) below:

in which formula (XXII):

-   -   R denotes a group chosen from:

aminoproml: —(CH₂)₃—NH2, aminoethyl —(CH₂)₂—NH₂, —(CH₂)₂—NH—C(O)—NH₂ and

The compounds corresponding to formula (XXII) are histidine, lysine, arginine, ornithine and citrulline.

The organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may be made in particular of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may be made especially of carnosine, anserine and baleine.

The organic amine is chosen from compounds comprising a guanidine function. As amines of this type that may be used in the present invention, besides arginine, which has already been mentioned as an amino acid, mention may be made especially of creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, N-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

Mention may be made in particular of the use of guanidine carbonate or monoethanolamine hydrochloride as hybrid compounds.

The composition of the invention preferably contains one or more alkanolamines and/or one or more basic amino acids, more advantageously one or more alkanolamines. More preferentially still, the organic amine is monoethanolamine.

According to one particular embodiment, the composition of the invention comprises, as alkaline agent, one or more alkanolamines.

Preferably, the alkanolamine is ethanolamine (or monoethanolamine).

In one variant of the invention, the composition comprises, as alkaline agent, one or more alkanolamines (preferably ethanolamine) and aqueous ammonia. In this variant, the alkanolamine(s) are present in a predominant amount relative to the aqueous ammonia.

Advantageously, the composition according to the invention has a content of alkaline agent(s) ranging from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight and better still from 1% to 10% by weight relative to the weight of the said composition.

v) At Least One Reducing Agent.

The composition of the invention comprises one or more reducing agents.

Preferably, the reducing agent(s) are chosen from thiols such as thioglycolic acid, thiolactic acid, 3-mercaptopropionic acid, thiomalic acid, 2,3-dimercaptosuccinic acid, cysteine, N-glycyl-L-cysteine, L-cysteinylglycine and also esters and salts thereof, thioglycerol, cysteamine and C₁-C₄ acyl derivatives thereof, N-mesylcysteamine, N-acetylcysteine, N-mercaptoalkylamides of sugars such as N-(mercapto-2-ethyl) gluconamide, pantetheine, N-(mercaptoalkyl)-ω-hydroxyalkylamides, for example those described in patent application EP-A-354 835, N-mono- or N,N-dialkylmercapto-4-butyramides, for example those described in patent application EP-A-368 763, aminomercaptoalkyl amides, for example those described in patent application EP-A-432 000, N-(mercaptoalkyl)succinamic acids and N-(mercaptoalkyl)succinimides, for example those described in patent application EP-A-465 342, alkylamino mercaptoalkyl amides, for example those described in patent application EP-A-514 282, the azeotropic mixture of 2-hydroxypropyl thioglycolate and of (2-hydroxy-1-methyl)ethyl thioglycolate as described in patent application FR-A-2 679 448, mercaptoalkylamino amides, for example those described in patent application FR-A-2 692 481, and N-mercaptoalkylalkanediamides, for example those described in patent application EP-A-653 202.

The reducing agent may alternatively be chosen from hydrides such as sodium or potassium borohydride or alkali metal or alkaline-earth metal sulfites or bisulfites; or alternatively from phosphorus derivatives such as phosphines or phosphites.

The reducing agent(s) are preferably chosen from thiols.

The preferred reducing agents are thioglycolic acid and cysteine, or salts thereof. The reducing agent is preferably used as an aqueous solution.

In general, the concentration of reducing agent(s) is inclusively between 0.01% and 30% by weight, preferably between 0.1% and 25% by weight and more particularly between 0.5% and 10% by weight relative to the total weight of the composition applied to the keratin fibres.

vi) Optionally at Least One Oxidizing Agent

The composition according to the invention may also comprise one or more chemical oxidizing agent(s). The term “chemical oxidizing agent” means an oxidizing agent other than atmospheric oxygen.

The chemical oxidizing agents are for example chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof and percarbonates of alkali metals or alkaline-earth metals. Advantageously, the oxidizing agent is hydrogen peroxide.

The content of oxidizing agent(s) more particularly represents from 0.1% to 20% by weight and preferably from 0.5% to 10% by weight relative to the weight of the composition containing them.

vii) Optionally at Least One Thickening Organic Polymer;

The composition according to the invention may contain vii) one or more thickening organic polymers.

the term “thickening polymer” means a polymer which, when introduced at 1% by weight in an aqueous solution or an aqueous-alcoholic solution containing 30% ethanol, and at pH 7, or in an oil chosen from liquid petroleum jelly, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps and preferably of at least 500 cps, at 25° C. and at a shear rate of 1 s⁻¹. This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like). The thickening polymers may thicken the aqueous phase and/or the fatty phase, preferentially the aqueous phase.

the term “organic thickening polymer” means a thickening polymer as defined previously, which is formed from carbon and hydrogen, and possibly nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine or bromine, and also phosphorus, alkali metals such as sodium or potassium, or alkaline-earth metals such as magnesium or calcium. The organic polymers according to the invention do not comprise silicon.

The organic thickening polymers according to the invention may be of natural or synthetic origin.

The thickening polymers may be anionic, cationic, amphoteric or nonionic associative or non-associative polymers.

Aqueous-phase-thickening polymers that may be mentioned include non-associative thickening polymers bearing sugar units.

For the purposes of the present invention, the term “sugar unit” means a unit derived from a carbohydrate of formula C_(n)(H₂O)_(n-1) or (CH₂O)_(n), which may be optionally modified by substitution and/or by oxidation and/or by dehydration.

The sugar units that may be included the composition of the thickening polymers of the invention are preferably derived from the following sugars:

-   -   glucose;     -   galactose;     -   arabinose;     -   rhamnose;     -   mannose;     -   xylose;     -   fucose;     -   anhydrogalactose;     -   galacturonic acid;     -   glucuronic acid;     -   mannuronic acid;     -   galactose sulfate;     -   anhydrogalactose sulfate and     -   fructose.

Thickening polymers of the invention that may especially be mentioned include native gums such as:

a) tree or shrub exudates, including: gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid), ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);

-   -   karaya gum (polymer derived from galacturonic acid, galactose,         rhamnose and glucuronic acid);     -   gum tragacanth (or tragacanth) (polymer of galacturonic acid,         galactose, fucose, xylose and arabinose);

b) gums derived from algae, including:

-   -   agar (polymer derived from galactose and anhydrogalactose);     -   alginates (polymers of mannuronic acid and of glucuronic acid);     -   carrageenans and furcellerans (polymers of galactose sulfate and         of anhydrogalactose sulfate);

c) gums derived from seeds or tubers, including:

-   -   guar gum (polymer of mannose and galactose);     -   locust bean gum (polymer of mannose and galactose);     -   fenugreek gum (polymer of mannose and galactose);     -   tamarind gum (polymer of galactose, xylose and glucose);     -   konjac gum (polymer of glucose and mannose);

d) microbial gums, including:

-   -   xanthan gum (polymer of glucose, mannose acetate,         mannose/pyruvic acid and glucuronic acid);     -   gellan gum (polymer of partially acylated glucose, rhamnose and         glucuronic acid);     -   scleroglucan gum (glucose polymer);

e) plant extracts, including:

-   -   cellulose (glucose polymer);     -   starch (glucose polymer).     -   inulin.

These polymers may be physically or chemically modified. A physical treatment that may especially be mentioned is the temperature.

Chemical treatments that may be mentioned include esterification, etherification, amidation and oxidation reactions. These treatments can lead to polymers that may especially be nonionic, anionic or amphoteric.

Preferably, these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses.

The nonionic guar gums that may be used according to the invention may be modified with C₁-C₆ (poly)hydroxyalkyl groups.

Among the C₁-C₆ (poly)hydroxyalkyl groups that may be mentioned, for example, are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the prior art and can be prepared, for example, by reacting the corresponding alkene oxides such as, for example, propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

The degree of hydroxyalkylation preferably ranges from 0.4 to 1.2, and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120 by the company Rhodia Chimie.

The botanical origin of the starch molecules used in the present invention may be cereals or tubers. Thus, the starches are chosen, for example, from corn starch, rice starch, cassaya starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch.

The starches may be chemically or physically modified especially by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.

Distarch phosphates or compounds rich in distarch phosphate will preferentially be used, for instance the products sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassaya distarch phosphate), Prejel TK1 (gelatinized cassaya distarch phosphate) and Prejel 200 (gelatinized acetyl cassaya distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized corn distarch phosphate).

According to the invention, amphoteric starches may also be used, these amphoteric starches comprising one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be linked to the same reactive site of the starch molecule or to different reactive sites; they are preferably linked to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type, preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type.

The starch molecules may be derived from any plant source of starch, especially such as corn, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use the starch hydrolysates mentioned above. The starch is preferably derived from potato.

The non-associative thickening polymers of the invention may be cellulose-based polymers not comprising any C₁₀-C₃₀ fatty chains in their structure.

According to the invention, the term “cellulose-based polymer” means any polysaccharide compound bearing in its structure sequences of glucose residues connected via β-1,4 bonds; besides unsubstituted celluloses, the cellulose derivatives may be anionic, cationic, amphoteric or nonionic;

Thus, the cellulose-based polymers of the invention may be chosen from unsubstituted celluloses, including those in a monocrystalline form, and cellulose ethers.

Among these cellulose-based polymers, cellulose ethers, cellulose esters and cellulose ester ethers are distinguished.

Among the cellulose esters are inorganic esters of cellulose (cellulose nitrates, sulfates, phosphates, etc.), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates and acetatetrimellitates, etc.), and mixed organic/inorganic esters of cellulose, such as cellulose acetatebutyrate sulfates and cellulose acetatepropionate sulfates. Among the cellulose ester ethers, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

Among the nonionic cellulose ethers not containing a C₁₀-C₃₀ fatty chain, i.e. “Non-associative”, mention may be made of (C₁-C₄)alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Ethocel Standard 100 Premium from Dow Chemical); (poly)hydroxy(C₁-C₄)alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR sold by Aqualon) and hydroxypropylcelluloses (for example Klucel EF from Aqualon); mixed celluloses (poly) hydroxy(C₁-C₄)alkyl(C₁-C₄)alkylcelluloses such as hydroxypropyl methylcelluloses (for example Methocel E4M from Dow Chemical), hydroxyethyl methylcelluloses, hydroxyethyl methylcelluloses (for example Bermocoll E 481 FQ from Akzo Nobel) and hydroxybutyl methylcelluloses.

Among the anionic cellulose ethers not containing a fatty chain, mention may be made of (poly)carboxy(C₁-C₄)alkylcelluloses, and salts thereof. Examples that may be mentioned include carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.

Among the cationic cellulose ethers not containing a fatty chain, mention may be made of cationic cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and disclosed in particular in U.S. Pat. No. 4,131,576, such as (poly)hydroxy(C₁-C₄)alkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted in particular with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat® L 200 and Celquat® H 100 by the company National Starch.

Among the nonassociative thickening polymers not bearing sugar units that may be used, mention may be made of crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof.

A first family of nonassociative thickening polymers that is suitable for use is represented by crosslinked acrylic acid homopolymers.

Among the homopolymers of this type, mention may be made of those crosslinked with an allyl alcohol ether of the sugar series, such as, for example, the products sold under the names Carbopol 980, 981, 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA.

The nonassociative thickening polymers may also be crosslinked (meth)acrylic acid copolymers, such as the polymer sold under the name Aqua SF1 by the company Noveon.

The nonassociative thickening polymers may be chosen from crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and the crosslinked acrylamide copolymers thereof.

Among the partially or totally neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of acrylamide, mention may be made in particular of the product described in Example 1 of document EP 503 853, and reference may be made to said document as regards these polymers.

The composition may similarly comprise, as nonassociative thickening polymers, ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide.

Among the ammonium acrylate homopolymers that may be mentioned is the product sold under the name Microsap PAS 5193 by the company Hoechst. Among the copolymers of ammonium acrylate and of acrylamide that may be mentioned is the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst. Reference may be made especially to documents FR 2 416 723, U.S. Pat. No. 2,798,053 and U.S. Pat. No. 2,923,692 as regards the description and preparation of such compounds.

Among the aqueous-phase thickening polymers, mention may also be made of the non-cellulose-based associative polymers that are well known to those skilled in the art and especially of nonionic, anionic, cationic or amphoteric nature.

It is recalled that “associative polymers” are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

The term “hydrophobic group” means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.

Among the associative polymers of anionic type that may be mentioned are:

-   -   (a) those comprising at least one hydrophilic unit and at least         one fatty-chain allyl ether unit, more particularly those whose         hydrophilic unit is formed by an ethylenic unsaturated anionic         monomer, more particularly a vinylcarboxylic acid and most         particularly an acrylic acid or a methacrylic acid or mixtures         thereof.

Among these anionic associative polymers, those that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether, and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

Among the latter polymers, those most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), in particular those sold by the company Ciba under the names Salcare SC 80® and Salcare SC 90®, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10);

-   -   (b) polymers comprising i) at least one hydrophilic unit of         unsaturated olefinic carboxylic acid type, and ii) at least one         hydrophobic unit of the type such as a (C₁₀-C₃₀) alkyl ester of         an unsaturated carboxylic acid.

(C₁₀-C₃₀)alkyl esters of unsaturated carboxylic acids that are useful in the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example, according to U.S. Pat. No. 3,915,921 and U.S. Pat. No. 4,509,949.

Among the anionic associative polymers of this type, use will be made more particularly of those formed from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C₁₀-C₃₀ alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those formed from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C₁₀-C₃₀ alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.

Among the said above polymers, those most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1®, Pemulen TR2® and Carbopol 1382®, and even more preferentially Pemulen TR1®, and the product sold by the company SEPPIC under the name Coatex SX®.

Mention may also be made of the acrylic acid/lauryl methacrylate/vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.

-   -   (c) maleic anhydride/C₃₀-C₃₈ α-olefin/alkyl maleate terpolymers,         such as the product (maleic anhydride/C₃₀-C₃₈ α-olefin/isopropyl         maleate) sold under the name Performa V 1608® by the company         Newphase Technologies.     -   (d) acrylic terpolymers comprising:         -   i) about 20% to 70% by weight of an α,β-monoethylenically             unsaturated carboxylic acid [A],         -   ii) about 20% to 80% by weight of an α,β-monoethylenically             unsaturated non-surfactant monomer other than [A],         -   iii) about 0.5% to 60% by weight of a nonionic monourethane             which is the product of reaction of a monohydric surfactant             with a monoisocyanate containing monoethylenic unsaturation,             such as those described in patent application EP-A-0 173 109             and more particularly the terpolymer described in Example 3,             namely a methacrylic acid/methyl acrylate/behenyl alcohol             dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40             EO) terpolymer, as an aqueous 25% dispersion.     -   (e) copolymers comprising among their monomers an         α,β-monoethylenically unsaturated carboxylic acid and an ester         of an α,β-monoethylenically unsaturated carboxylic acid and of         an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of an α,β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄ alcohol.

An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Röhm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer.

-   -   (f) amphiphilic polymers comprising at least one ethylenically         unsaturated monomer bearing a sulfonic group, in free or         partially or totally neutralized form and comprising at least         one hydrophobic part. These polymers may be crosslinked or         noncrosslinked. They are preferably crosslinked.

The ethylenically unsaturated monomers bearing a sulfonic group are especially chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(C₁-C₂₂)alkylsulfonic acids, N—(C₁-C₂₂)alkyl(meth)acrylamido(C₁-C₂₂)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.

Use will more preferably be made of (meth)acrylamido(C₁-C₂₂)alkylsulfonic acids, such as, for example, acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof.

2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will more particularly be used.

The amphiphilic polymers in accordance with the invention may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C₆-C₂₂ n-monoalkylamine or di-n-alkylamine, and such as those described in Patent Application WO 00/31154. These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

The preferred polymers of this family are chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer.

These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

These copolymers are described especially in patent application EP-A-750 899, U.S. Pat. No. 5,089,578 and in the following Yotaro Morishima publications:

-   Self-assembling amphiphilic polyelectrolytes and their     nanostructures—Chinese Journal of Polymer Science Vol. 18, No. 40     (2000), 323-336; -   Micelle formation of random copolymers of sodium     2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant     macromonomer in water as studied by fluorescence and dynamic light     scattering—Macromolecules, Vol. 33, No. 10 (2000), 3694-3704; -   Solution properties of micelle networks formed by nonionic moieties     covalently bound to a polyelectrolyte: salt effects on rheological     behavior—Langmuir, Vol. 16, No. 12, (2000) 5324-5332; -   Stimuli responsive amphiphilic copolymers of sodium     2-(acrylamido)-2-methylpropanesulfonate and associative     macromonomers—Polym. Preprint, Div. Polym. Chem., 40(2), (1999),     220-221.

Among these polymers, mention may be made of:

-   -   copolymers, which may or may not be crosslinked and which may or         may not be neutralized, comprising from 15 to 60% by weight of         AMPS units and from 40 to 85% by weight of         (C₈-C₁₆)alkyl(meth)acrylamide units or of         (C₈-C₁₆)alkyl(meth)acrylate units, with respect to the polymer,         such as those described in Application EP-A-750 899;     -   terpolymers comprising from 10 mol % to 90 mol % of acrylamide         units, from 0.1 mol % to 10 mol % of AMPS units and from 5 mol %         to 80 mol % of n-(C₆-C₁₈)alkylacrylamide units, such as those         described in U.S. Pat. No. 5,089,578.

Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.

Among the cationic associative polymers that may be mentioned are:

(I) cationic associative polyurethanes;

(II) the compound sold by the company Noveon under the name Aqua CC and which corresponds to the INCI name Polyacrylate-1 Crosspolymer.

Polyacrylate-1 Crosspolymer is the product of polymerization of a monomer mixture comprising:

-   -   a di(C₁-C₄ alkyl)amino(C₁-C₆ alkyl) methacrylate,     -   one or more C₁-C₃₀ alkyl esters of (meth)acrylic acid,     -   a polyethoxylated C₁₀-C₃₀ alkyl methacrylate (20-25 mol of         ethylene oxide units),     -   a 30/5 polyethylene glycol/polypropylene glycol allyl ether,     -   a hydroxy(C₂-C₆ alkyl) methacrylate, and     -   an ethylene glycol dimethacrylate.

(III) quaternized (poly)hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternized alkylhydroxyethylcelluloses containing C₈-C₃₀ fatty chains that may be mentioned include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (C₁₂ alkyl) and Quatrisoft LM-X 529-8® (C₁₈ alkyl) sold by the company Aqualon, and the products Crodacel QM®, Crodacel QL® (C₁₂ alkyl) and Crodacel QS® (C₁₈ alkyl) sold by the company Croda, and the product Softcat SL 100® sold by the company Aqualon.

(IV) cationic polyvinyllactam polymers.

Such polymers are described, for example, in patent application WO-00/68282.

As cationic poly(vinyllactam) polymers according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidoprop ylammonium tosylate terpolymers, vinyl pyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamidopropyl ammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopropyla mmonium tosylate or chloride terpolymers are used in particular.

The amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. Even more particularly, the ones that are preferred are those prepared from or comprising 1 to 20 mol %, preferably 1.5 to 15 mol % and even more particularly 1.5 to 6 mol % of fatty-chain monomer relative to the total number of moles of monomers.

Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/44012.

Among the amphoteric associative polymers according to the invention, the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.

The associative polymers of nonionic type that may be used according to the invention are preferably chosen from:

-   -   (a) copolymers of vinylpyrrolidone and of fatty-chain         hydrophobic monomers, of which examples that may be mentioned         include:         -   the products Antaron V216® and Ganex V216®             (vinylpyrrolidone/hexadecene copolymer) sold by the company             ISP,         -   the products Antaron V220® and Ganex V220®             (vinylpyrrolidone/eicosene copolymer) sold by the company             ISP.     -   (b) copolymers of C₁-C₆ alkyl methacrylates or acrylates and of         amphiphilic monomers comprising at least one fatty chain, such         as, for example, the oxyethylenated methyl acrylate/stearyl         acrylate copolymer sold by the company Goldschmidt under the         name Antil 208®.     -   (c) copolymers of hydrophilic methacrylates or acrylates and of         hydrophobic monomers comprising at least one fatty chain, for         instance the polyethylene glycol methacrylate/lauryl         methacrylate copolymer.     -   (d) polyurethane polyethers comprising in their chain both         hydrophilic blocks usually of polyoxyethylenated nature and         hydrophobic blocks, which may be aliphatic sequences alone         and/or cycloaliphatic and/or aromatic sequences.     -   (e) polymers with an aminoplast ether backbone containing at         least one fatty chain, such as the Pure Thix® compounds sold by         the company Sud-Chemie.     -   (f) celluloses or derivatives thereof, modified with groups         comprising at least one fatty chain, such as alkyl, arylalkyl or         alkylaryl groups or mixtures thereof in which the alkyl groups         are of C₈, and in particular:     -   * nonionic alkylhydroxyethylcelluloses such as the products         Natrosol Plus Grade 330 CS and Polysurf 67 (C₁₆ alkyl) sold by         the company Aqualon;     -   * nonionic nonoxynylhydroxyethylcelluloses such as the product         Amercell HM-1500 sold by the company Amerchol;     -   * nonionic alkylcelluloses such as the product Bermocoll EHM 100         sold by the company Berol Nobel;     -   (g) associative guar derivatives, for instance hydroxypropyl         guars modified with a fatty chain, such as the product Esaflor         HM 22 (modified with a C₂₂ alkyl chain) sold by the company         Lamberti; the product Miracare XC 95-3 (modified with a C₁₄         alkyl chain) and the product RE 205-146 (modified with a C₂₀         alkyl chain) sold by Rhodia Chimie.

Preferably, the polyurethane polyethers comprise at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be included. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.

The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example multiblock copolymer). These same polymers may also be graft polymers or star polymers.

The nonionic fatty-chain polyurethane polyethers may be triblock copolymers in which the hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylene groups. The nonionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, whence arises the name.

By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.

As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, it is also possible to use Rheolate 205® containing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®.

Mention may also be made of the product Elfacos T210® containing a C₁₂₋₁₄ alkyl chain, and the product Elfacos T212® containing a C₁₈ alkyl chain, from Akzo.

The product DW 1206B® from Röhm & Haas containing a C₂₀ alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned are Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox. The products DW 1206F and DW 1206J sold by the company Röhm & Haas may also be used.

The polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Formum, J. Bakke and Fk. Hansen—Colloid Polym. Sci. 271, 380.389 (1993).

It is even more particularly preferred to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane polyethers are sold especially by the company Röhm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].

Use may also be made of fatty-phase-thickening polymers.

Preferably, the polymers for structuring the oily phase via physical interactions are chosen from polyamides, silicone polyamides, saccharide or polysaccharide mono- or polyalkyl esters, N-acylamino acid amide derivatives, and copolymers comprising an alkylene or styrene block, these copolymers possibly being diblock, triblock, multiblock or radial-block polymers, also known as star copolymers, or alternatively comb polymers.

1) Polymers Bearing at Least One Crystallizable Block in the Backbone

These are also polymers that are soluble or dispersible in the oil or fatty phase by heating above their melting point m.p. These polymers are especially block copolymers consisting of at least two blocks of different chemical nature, one of which is crystallizable.

As polymers bearing in the backbone at least one crystallizable block that are suitable for use in the invention, mention may be made of:

i). the polymers defined in document U.S. Pat. No. 5,156,911;

ii). block copolymers of olefin or of cycloolefin containing a crystallizable chain, for instance those derived from the block polymerization of:

-   -   cyclobutene, cyclohexene, cyclooctene, norbornene (i.e.         bicyclo(2,2,1)-2-heptene), 5-methylnorbornene,         5-ethylnorbornene, 5,6-dimethyl-norbornene,         5,5,6-trimethylnorbornene, 5-ethylidenenorbornene,         5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene,         1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydro-naphthalene,         dicyclopentadiene, and mixtures thereof,     -   with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene,         4-methyl-1-pentene, 1-octene, 1-decene or 1-eicosene, or         mixtures thereof. These block copolymers may be in particular         (ethylene/norbornene) block copolymers and         (ethylene/propylene/ethylidenenorbornene) block terpolymers.

Those resulting from the block copolymerization of at least two C₂-C₁₆, and better still C₂-C₁₂, α-olefins such as those mentioned above and in particular block bipolymers of ethylene and of 1-octene may also be used.

Copolymers containing at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers may also contain two crystallizable blocks of different chemical nature. The preferred copolymers are those that simultaneously contain at room temperature a crystallizable block and an amorphous block that are both hydrophobic and lipophilic, sequentially distributed; mention may be made, for example, of polymers containing one of the crystallizable blocks and one of the amorphous blocks below:

-   -   Block that is crystallizable by nature: a) of polyester type,         for instance poly(alkylene terephthalate), b) of polyolefin         type, for instance polyethylenes or polypropylenes.     -   Amorphous and lipophilic block, for instance: amorphous         polyolefins or copoly(olefin)s such as poly(isobutylene),         hydrogenated polybutadiene or hydrogenated poly(isoprene).

As examples of such copolymers containing a crystallizable block and an amorphous block, mention may be made of:

a) poly(δ-caprolactone)-b-poly(butadiene) block copolymers, preferably used hydrogenated, such as those described in the article Melting behaviour of poly(δ-caprolactone)-block-polybutadiene copolymers from S. Nojima, Macromolecules, 32, 3727-3734 (1999),

b) the hydrogenated block or multiblock poly(butylene terephthalate)-b-poly(isoprene) block copolymers cited in the article Study of morphological and mechanical properties of PP/PBT by B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995),

c) the poly(ethylene)-b-copoly(ethylene/propylene) block copolymers cited in the articles Morphology of semi-crystalline block copolymers of ethylene-(ethylene-alt-propylene) by P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) and Polymer aggregates with crystalline cores: the system poly(ethylene)poly(ethylene-propylene) P. Richter et al., Macromolecules, 30, 1053-1068 25 (1997).

d) the poly(ethylene)-b-poly(ethylethylene) block copolymers mentioned in the general article Crystallization in block copolymers by I. W. Hamley, Advances in Polymer Science, vol. 148, 113-137 (1999).

The semi-crystalline polymers that may be used in the context of the invention may be non-crosslinked or partially crosslinked, provided that the degree of crosslinking does not impede their dissolution or dispersion in the liquid oily phase by heating above their melting point. It may then be a case of chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It may also be a case of physical crosslinking, which may then be due either to the establishment of bonds of hydrogen or dipolar type between groups borne by the polymer, for instance dipolar interactions between carboxylate ionomers, these interactions being in small amount and borne by the polymer backbone; or due to a phase separation between the crystallizable blocks and the amorphous blocks borne by the polymer.

Preferably, the semi-crystalline polymers that are suitable for the invention are non-crosslinked.

As particular examples of semi-crystalline polymers that may be used in the composition according to the invention, mention may be made of the Intelimer® products from the company Landec described in the brochure “Intelimer® polymers”. These polymers are in solid form at room temperature (25° C.). They bear crystallizable side chains and contain the monomer. Mention may be made especially of “Landec IP22®”, with a melting point m.p. of 56° C., which is a viscous, impermeable, non-tacky product at room temperature.

It is also possible to use the semi-crystalline polymers described in Examples 3, 4, 5, 7 and 9 of U.S. Pat. No. 5,156,911, resulting from the copolymerization of acrylic acid and of C₅ to C₁₆ alkyl (meth)acrylate, such as those resulting from the copolymerization:

-   -   of acrylic acid, of hexadecyl acrylate and of isodecyl acrylate         in a 1/16/3 ratio,     -   of acrylic acid and of pentadecyl acrylate in a 1/19 ratio,     -   of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in         a 2.5/76.5/20 ratio,     -   of acrylic acid, of hexadecyl acrylate and of methyl acrylate in         a 5/85/10 ratio,     -   of acrylic acid and of octadecyl (meth)acrylate in a 2.5/97.5         ratio.

It is also possible to use the polymer “Structure O” sold by the company National Starch, such as the product described in document U.S. Pat. No. 5,736,125, of m.p. 44° C., and also semi-crystalline polymers containing crystallizable side chains comprising fluoro groups as described in Examples 1, 4, 6, 7 and 8 of document WO-A-01/19333.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of stearyl acrylate and of acrylic acid or of NVP, or by copolymerization of behenyl acrylate and of acrylic acid or NVP, as described in document U.S. Pat. No. 5,519,063 or EP-A-0 550 745.

According to one particular embodiment variant, the semi-crystalline polymers that are suitable for use in the present invention are especially alkyl acrylates, among which mention may be made of the Landec copolymers:

-   -   Doresco IPA 13-10: polystearyl acrylate, m.p. of 49° C. and MW         of 145 000;     -   Doresco IPA 13-3®: polyacrylate/methacrylic acid, m.p. of 65° C.         and MW of 114 000;     -   Doresco IPA 13-4®: polyacrylate/vinylpyrrolidone, m.p. of 44° C.         and MW of 387 000;     -   Doresco IPA13-5®: polyacrylate/hydroxyethyl methacrylate, m.p.         of 47° C. and MW of 397 600;     -   Doresco IPA 13-6®: polybehenyl acrylate, m.p. of 66° C.

2) Non-Silicone Polyamides

The particular polyamides used in the composition according to the invention are preferably those described in document U.S. Pat. No. 5,783,657 from the company Union Camp.

Each of these polyamides especially satisfies formula (XXXVII) below:

in which formula (XXII):

-   -   n denotes a whole number of amide units such that the number of         ester groups represents from 10% to 50% of the total number of         ester and amide groups;     -   R¹ is independently in each case an alkyl or alkenyl group         containing at least 4 carbon atoms and especially from 4 to 24         carbon atoms;     -   R² represents independently in each case a C₄ to C₅₅         hydrocarbon-based group, on condition that 50% of the groups R₂         represent a C_(m) to C₅₋₅ hydrocarbon-based group;     -   R³ represents independently in each case an organic group         bearing at least two carbon atoms, hydrogen atoms and optionally         one or more oxygen or nitrogen atoms; and     -   R⁴ represents independently in each case a hydrogen atom, a C₁         to C₁₀ alkyl group or a direct bond to R₃ or to another R₄ such         that the nitrogen atom to which are attached both R₃ and R₄         forms part of a heterocyclic structure defined by R₄—N—R₃, with         at least 50% of the groups R₄ representing a hydrogen atom.

In particular, the ester groups of this polyamide represent from 15% to 40% and at best from 20% to 35% of the total number of ester and amide groups. Furthermore, n advantageously represents an integer ranging from 1 to 10 and better still from 1 to 5, limits inclusive.

Preferably, R¹ is a C₁₂ to C₂₂ and preferably C₁₆ to C₂₂ alkyl group. Advantageously, R² may be a C₁₀ to C₄₂ hydrocarbon-based (alkylene) group. Preferably, at least 50% and better still at least 75% of the groups R² are groups containing from 30 to 42 carbon atoms. The other groups R² are C₄ to C₁₉ and better still C₄ to C₁₂ hydrogen-containing groups. Preferably, R³ represents a C₂ to C₃₆ hydrocarbon-based group or a polyoxyalkylene group and R⁴ represents a hydrogen atom. Preferably, R³ represents a C₂ to C₁₂ hydrocarbon-based group. The hydrocarbon-based groups may be linear, cyclic or branched, and saturated or unsaturated groups. Moreover, the alkyl and alkylene groups may be linear or branched, and saturated or unsaturated groups.

The thickening of the oily phase may be obtained by means of one or more polyamides defined above. In general, these polyamides are in the form of mixtures, these mixtures also possibly containing a synthetic product corresponding to a polyamide as defined above with n being 0, i.e. a diester.

As structuring polyamides that may be used in the invention, mention may also be made of polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds containing, respectively, more than two carboxyl groups and more than two amine groups), the carboxyl and amine groups of adjacent individual units being condensed in the form of an amide bond. These polyamide resins are especially the products sold under the brand name Versamid® by the companies General Mills, Inc. and Henkel Corp., under the brand name Onamid®, especially Onamid S or C. These resins have a weight-average molecular mass ranging from 6000 to 9000. For further information regarding these polyamides, reference may be made to U.S. Pat. No. 3,645,705 and U.S. Pat. No. 3,148,125. Use is made more especially of Versamid® 30 or 744.

It is also possible to use the polyamides sold or manufactured by the company Arizona under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) and the product sold under the reference Macromelt 6212 by the company Henkel. For further information regarding these polyamides, reference may be made to document U.S. Pat. No. 5,500,209.

As examples of structuring polyamides that may be used in the composition according to the invention, mention may also be made of the commercial products sold or manufactured by the company Arizona Chemical under the names Uniclear 80 and Uniclear 100. They are sold, respectively, in the form of an 80% (active material) gel and a 100% (active material) gel in a mineral oil. They have a softening point of from 88 to 105° C. These commercial products are a mixture of copolymers of a C36 diacid coupled with ethylenediamine, having an average molecular mass of about 6000. The terminal ester groups result from the esterification of the remaining acid end groups with cetyl alcohol, stearyl alcohol or mixtures thereof (also known as cetylstearyl alcohol).

2) Saccharide or Polysaccharide Mono- or Polyalkyl Esters

Among the saccharide or polysaccharide monoalkyl or polyalkyl esters that are suitable for use in the invention, mention may be made of dextrin or inulin alkyl or polyalkyl esters.

It may especially be a dextrin mono- or polyester of at least one fatty acid corresponding especially to formula (XXIII) below:

in which formula (XXIII):

-   -   n is an integer ranging from 3 to 200, especially ranging from         20 to 150 and in particular ranging from 25 to 50,     -   R₁, R₂ and R₃, which may be identical or different, are chosen         from hydrogen and an acyl group (R—C(O)—) in which the radical R         is a linear or branched, saturated or unsaturated         hydrocarbon-based group containing from 7 to 29, in particular         from 7 to 21, especially from 11 to 19, more particularly from         13 to 17, or even 15, carbon atoms, with the proviso that at         least one of the said radicals R₁, R₂ or R₃ is other than         hydrogen.

In particular, R₁, R₂ and R₃ may represent hydrogen or an acyl group (R—C(O)—) in which R is a hydrocarbon-based radical as defined above, with the proviso that at least two of the said radicals R₁, R₂ and R₃ are identical and other than hydrogen.

The radicals R₁, R₂ and R₃ may all contain an acyl group (R—C(O)), which is identical or different and especially identical.

In particular, n mentioned above advantageously ranges from 25 to 50 and is especially equal to 38 in the general formula of the saccharide ester that may be used in the present invention.

When the radicals R₁, R₂ and/or R₃, which may be identical or different, contain an acyl group (R—C(O)), these radicals may be chosen especially from caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, 2-ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic and stearolic radicals, and mixtures thereof.

Preferably, at least one dextrin palmitate is used as fatty acid ester of dextrin. This ester may be used alone or as a mixture with other esters.

Advantageously, the fatty acid ester of dextrin has a degree of substitution of less than or equal to 2.5, especially ranging from 1.5 to 2.5 and preferably from 2 to 2.5 on the basis of one glucose unit. The weight-average molecular weight of the dextrin ester may in particular be from 10 000 to 150 000, especially from 12 000 to 100 000 and even from 15 000 to 80 000.

Dextrin esters, in particular dextrin palmitates, are commercially available under the name Rheopearl TL or Rheopearl KL by the company Chiba Flour.

3) N-Acylamino Acid Amide Derivatives

The N-acylamino acid amides that may be used are, for example, diamides from the combination of an N-acylamino acid with amines comprising from 1 to 22 carbon atoms, such as those described in document FR 2 281 162. They are, for example, alkylglutamic acid amide derivatives such as the laurylglutamic acid dibutylamide sold by the company Ajinomoto under the name Gelling Agent GP-1, or alternatively the 2-ethylhexylglutamic acid dibutylamide sold by the company Ajinomoto under the name Gelling Agent GA-01.

4) Copolymers Comprising an Alkylene or Styrene Block

The copolymers may have a comb or the block structure of diblock, triblock, multiblock and/or radial or star type and may comprise at least two thermodynamically incompatible segments.

The structuring agent may comprise, for example, a styrene segment as described in patent applications EP 0 497 144, WO 98/42298, U.S. Pat. No. 6,225,690, U.S. Pat. No. 6,174,968 and U.S. Pat. No. 6,225,390, an ethylene/butylene segment or an ethylene/propylene segment as described in U.S. Pat. No. 6,225,690, U.S. Pat. No. 6,174,968 and U.S. Pat. No. 6,225,390, a butadiene segment, an isoprene segment, a polyvinyl segment, for instance polyalkyl (meth)acrylate or polyvinyl alcohol or polyvinyl acetate, a silicone segment as described in U.S. Pat. No. 5,468,477 and U.S. Pat. No. 5,725,882, or a combination of these segments.

A diblock copolymer is usually defined as being of A-B type in which a hard segment (A) is followed by a soft segment (B).

A triblock copolymer is usually defined as being of A-B-A type or as a ratio of a hard segment, a soft segment and a hard segment.

A multiblock, radial or star copolymer may comprise any type of combination of hard segments and soft segments, with the proviso that the characteristics of the hard segments and of the soft segments are conserved.

An example of hard segments of block copolymers that may be mentioned is styrene, and examples of soft segments of block copolymers that may be mentioned include ethylene, propylene and butylene, and a combination thereof.

The triblock copolymers, and especially those of polystyrene/polyisoprene or polystyrene/polybutadiene type, which are suitable for use in the invention may be those sold under the reference Luvitol HSB by the company BASF. Mention may also be made of triblock copolymers of polystyrene/copoly(ethylene-propylene) or polystyrene/copoly(ethylene-butylene) type, such as those sold under the reference Kraton by the company Shell Chemical Co., or under the reference Gelled Permethyl 99 A by the company Penreco. Such triblock copolymers are particularly preferred according to the invention.

As a further example of block copolymers that may be suitable for use in the present invention, mention may also be made of the block copolymers sold under the reference Versagel by the company Penreco, those sold under the reference Kraton by the company Shell and those sold under the reference Gel Base by the company Brooks Industries.

Among the fatty-phase thickening polymers, polymers bearing in the backbone at least one crystallizable block are preferred.

The aqueous-phase or fatty-phase thickening polymers may be used alone or as mixtures in all proportions.

Preferably, the thickeners are aqueous-phase thickeners.

Preferably, the polymers in the cosmetic compositions in accordance with the present invention advantageously have in solution or in dispersion, at 1% active material in water, a viscosity, measured using a Rheomat RM 180 rheometer at 25° C., of greater than 0.1 ps and even more advantageously greater than 0.2 cp, at a shear rate of 200 s⁻¹.

According to one particular embodiment of the invention, the organic thickening polymer(s) are chosen from cellulose-based polymers.

The organic thickening polymer(s) are present in the composition according to the invention in a content ranging from 0.01% to 10% by weight and preferably from 0.1% to 5% by weight relative to the total weight of the composition.

viii) Adjuvants:

The composition comprising the ingredients i) to v) as defined previously may also contain various adjuvants conventionally used in hair dye compositions, such as anionic surfactants, nonionic surfactants other than the ethoxylated fatty alcohols ii), amphoteric or zwitterionic surfactants, or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral thickeners, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.

The above adjuvants are generally present in an amount, for each of them, inclusively between 0.01% and 20% by weight relative to the weight of the composition.

Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

ix) Additional Dyes:

The composition comprising the dye(s) bearing a disulfide, thiol or protected-thiol function especially of formula (I) as defined previously of the process of the invention may also contain one or more additional direct dyes other than the disulfide, thiol or protected-thiol direct dyes of formula (I) according to the invention. These direct dyes are chosen, for example, from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine, cyanine and methine direct dyes, and fluorescent dyes, other than the dyes of formula (I).

The composition comprising the dye(s) bearing a disulfide, thiol or protected thiol function especially of formula (I) as defined previously of the process of the invention may also contain one or more oxidation bases and/or one or more couplers conventionally used for the dyeing of keratin fibres.

Among the oxidation bases, mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.

Among these couplers, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.

The coupler(s) are each generally present in an amount inclusively between 0.001% and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.

The oxidation base(s) present in the dye composition are each generally present in an amount inclusively between 0.001% and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.

In general, the addition salts of the oxidation bases and couplers used in the context of the invention are especially chosen from the salts of addition with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the salts of addition with a base, such as alkali metal hydroxides, for instance sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

According to one particular embodiment, the composition of the process of the invention contains at least one oxidation base and optionally at least one coupler as defined above.

This embodiment may be implemented in the presence of one or more chemical oxidizing agents. The term “chemical oxidizing agent” means chemical oxidizing agents other than atmospheric oxygen, such as those described previously.

The use of hydrogen peroxide is particularly preferred.

The content of oxidizing agent(s) is generally inclusively between 1% and 40% by weight relative to the weight of the composition and preferably between 1% and 20% by weight relative to the weight of the composition containing them.

The pH:

The pH of the composition according to the invention is generally inclusively between 2 and 12 approximately and preferably between 3 and 11 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.

The pH of the composition is preferentially inclusively between 6 and 9, particularly between 7 and 9, and more particularly between 7.5 and 9.

Among the acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

Among the alkaline agents that may be mentioned, for example, are aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and other alkaline agents iv) as defined previously.

Forms of the Composition:

The dye composition comprising i) the dye(s) bearing a disulfide, thiol or protected-thiol function especially of formula (I) as defined previously and the ingredients ii), iii), iv) and v) as defined previously may be in various galenical forms, such as in the form of liquids, lotions, creams or gels, or in any other form that is suitable for dyeing keratin fibres. They may also be conditioned under pressure in an aerosol can in the presence of a propellant or in a non-aerosol can, and form a mousse.

2). DYEING PROCESSES OF THE INVENTION

The process for dyeing keratin fibres, especially dark keratin fibres, according to the invention comprises the step of applying to the keratin fibres:

-   -   i) at least one cationic direct dye bearing a disulfide         function, a thiol function or a protected-thiol function as         defined previously;     -   ii) at least one sparingly ethoxylated or non-ethoxylated fatty         alcohol as defined previously;     -   iii) at least one cationic surfactant as defined previously;     -   iv) at least one alkaline agent as defined previously;     -   v) at least one reducing agent as defined previously; and     -   vii) optionally at least one organic thickening polymer as         defined previously; the ingredients i) to v) and vii) possibly         being applied either together onto the said fibres or         separately.

When it is desired to lighten dark keratin fibres without the use of a chemical oxidizing agent, an ingredient i) that is fluorescent is used in the dye composition or the dyeing process. Preferentially, the fluorescent dyes of formula (I) are chosen from the dyes of formulae (XIII), (XIII′), (XIV), (XIV′), (XVa), (XV′a), (XV) to (XV′), (XVI), (XVI′), (XVIa) and (XVI′a) as defined previously. More particularly, the fluorescent dyes i) as defined previously used for lightening keratin fibres are chosen from compounds 44, 49, 49a and 55.

The dyeing process according to the invention may be performed in one step by applying to the keratin fibres the composition according to the invention comprising the ingredients i) to v) and optionally vii) as defined previously, in one or more steps.

According to one particular embodiment of the process of the invention, the reducing agent v) as defined previously may be applied as a pretreatment before the application of the dye composition containing the ingredients i) to iv) and optionally vii).

According to another interesting variant, the reducing composition comprising the reducing agent v) and the ingredients iv) and iii) as defined previously is applied to the keratin fibres as a pretreatment before the application of the dye composition comprising the ingredients i) and ii) and optionally vii) as defined previously.

According to another variant of the invention, the reducing composition comprising the reducing agent v) and the ingredient iv) as defined previously is applied to the keratin fibres as a pretreatment before the application of the dye composition comprising the ingredients i), ii) and iii) and optionally vii) as defined previously.

According to another variant of the invention, the reducing composition comprising the reducing agent v) and the ingredient iii) as defined previously is applied to the keratin fibres as a pretreatment before the application of the dye composition comprising the ingredients i), ii) and iv) and optionally vii) as defined previously.

According to another variant of the invention, the reducing composition comprising the reducing agent v) and the ingredient ii) as defined previously is applied to the keratin fibres as a pretreatment before the application of the dye composition comprising the ingredients i), iii) and iv) and optionally vii) as defined previously.

According to another particularly advantageous embodiment, the process of the invention comprises a first step of reducing pretreatment with a reducing composition that is applied to the keratin fibres, comprising the ingredients iv), v) and optionally ii) as defined previously, followed, in a second step, by the application of a dye composition comprising the ingredients i), ii) and iii) and optionally vii) as defined previously.

The reducing pretreatment may be of short duration, especially from 1 second to 30 minutes and preferably from 1 minute to 15 minutes, with one or more reducing agents as mentioned previously.

Between the reducing pretreatment step and the dyeing step using the composition comprising the ingredient i) as defined previously, the keratin fibres are preferentially rinsed with water.

The leave-on time of the dye composition, i.e. comprising the ingredient i) as defined previously, is inclusively between 5 minutes and 1 hour and preferably between 10 minutes and 40 minutes.

The dye composition, i.e. the composition comprising the ingredient i), is generally applied at room temperature. However, it may be applied at temperatures ranging from 20 to 180° C.

According to another variant, instead of using the reducing agent as a pretreatment, it is used as a post-treatment, after the application of the dye composition.

According to another particular dyeing process of the invention, the dyeing process does not comprise any reducing pretreatment or post-treatment step. In this case, the dyeing process comprises the step of applying the composition according to the invention, which comprises the ingredients i) to v) and optionally vii) as defined previously.

When the ingredient i) is a protected-thiol dye, i.e. the thiol dye of formula (I) as defined previously in which U═Y with Y being a protecting group, the process of the invention may be preceded by a deprotection step for restoring the SH function in situ.

By way of example, it is possible to deprotect the function S—Y of the dyes of the invention with Y being a protecting group, by adjusting the pH as follows:

Y: protecting group deprotection alkylcarbonyl, pH > 9 arylcarbonyl, pH > 9 alkoxycarbonyl, pH > 9 aryloxycarbonyl, pH > 9 arylalkoxycarbonyl, pH > 9 (di)(alkyl)aminocarbonyl, pH > 9 (alkyl)arylaminocarbonyl, pH > 9 optionally substituted aryl pH > 9 such as phenyl, 5-, 6- or 7-membered monocyclic pH > 9 heteroaryl such as oxazolium, 8- to 11-membered bicyclic pH > 9 heteroaryl such as benzimidazolium or benzoxazolium

The deprotection step may also be performed during a step of pretreatment of the hair, for instance the hair-reducing pretreatment.

A treatment with one or more chemical oxidizing agents may optionally be performed after the application of ingredients i) to iv) and optionally vii) as defined previously to the keratin fibres. To do this, a fixing composition comprising at least one cosmetic chemical oxidizing agent such as the ingredient vi) as defined previously and optionally the ingredient vii) as defined previously may be used. Thus, it may be chosen especially from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.

The leave-on time of the oxidizing (fixing) composition is inclusively between 1 second and 40 minutes and preferably between 15 seconds and 15 minutes.

Preferentially, the application of the oxidizing composition takes place after the application of the dye composition, i.e. the composition comprising the ingredient i) as defined previously and optionally the ingredient vii) as defined previously.

Between the dyeing step using the composition comprising the ingredient i) as defined previously and the fixing step, the keratin fibres are preferentially rinsed with water.

When the ingredients i) and v) and optionally vii) as defined previously are not in the same composition, the pH of the composition that contains i) is preferentially inclusively between 4 and 10 and particularly between 5 and 7; and the pH of the composition that contains v) is preferentially inclusively between 4 and 10 and particularly between 7 and 10.

The dyeing and/or lightening process according to the invention may be followed by shampooing with a standard shampoo and/or drying of the keratin fibres.

According to particularly advantageous embodiments, the process is performed in three different ways using compositions A, B and C in which:

-   -   the dye composition A contains:         -   i) at least one fluorescent disulfide dye in a concentration             inclusively between 0.01 g % and 5 g % and preferably             between 0.05 g % and 2 g %;         -   ii) at least one fatty alcohol preferentially chosen from             myristyl alcohol, stearyl alcohol and palmityl alcohol, in a             concentration inclusively between 0.05 g % and 10 g % and             preferably inclusively between 0.5 g % and 5 g %;         -   iii) at least one cationic surfactant preferably chosen from             quaternary ammonium salts containing one or more ester             functions, such as those of formula (XX) as defined             previously, in a concentration inclusively between 0.1 g %             and 40 g % and preferably between 1 g % and 15 g %;         -   the pH of composition A preferably being inclusively between             4 and 10, and more particularly between 5 and 7;     -   the reducing composition B comprises:         -   v) at least one thiol reducing agent in a concentration             preferably inclusively between 0.5 g % and 50 g % and more             particularly inclusively between 10 g % and 30 g %;         -   iv) at least one alkaline agent preferably comprising an             amine group, in a concentration preferably inclusively             between 0.1 g % and 30 g % and more particularly between 0.5             g % and 5 g %;         -   and optionally at least one fragrance in a concentration             preferably inclusively between 0.01 g % and 10 g % and more             particularly between 0.2 g % and 2 g %;             the pH of composition B preferably being inclusively between             5 and 12, and more particularly inclusively between 7 and             10;     -   the fixing composition C comprises: vi) at least one oxidizing         agent in a concentration preferably inclusively between 0.01 g %         and 30 g % and more particularly between 0.5 g % and 5 g %, the         pH of composition C preferably being inclusively between 1.5 and         7 and more particularly between 2 and 5;     -   it being understood that the fixing composition may also         comprise a thickening organic polymer vii) as defined         previously; just like compositions A and/or B.

Variant 1:

The dye composition A is mixed with the reducing composition B in the following proportions: 9 volumes of composition A are mixed with 1 volume of composition B in a bowl. The mixture is applied to the hair with a leave-on time preferably inclusively between 5 minutes and 1 hour and preferably between 10 minutes and 40 minutes. The hair is rinsed and is then optionally shampooed, shampooing preferably being performed, and the hair is then dried.

Variant 2:

The dyeing formula A is mixed with the reducing composition B in the following proportions: 9 volumes of composition A are mixed with 1 volume of composition B in a bowl. The mixture is applied to the hair with a leave-on time preferably inclusively between 5 minutes and 1 hour and more particularly inclusively between 10 minutes and 40 minutes.

The hair is optionally rinsed, preferably rinsed. The fixing composition C is then applied to the hair with a leave-on time preferably inclusively between 1 minutes and 30 hour and more particularly inclusively between 3 minutes and 10 minutes.

The hair is rinsed and is then optionally shampooed, shampooing preferably being performed, and the hair is then dried.

Variant 3:

The reducing formula is applied to the hair with a leave-on time preferably inclusively between 5 minutes and 1 hour and more particularly inclusively between 10 minutes and 40 minutes. The hair is optionally rinsed, preferably rinsed. The dye formula is applied to the hair with a leave-on time preferably inclusively between 5 minutes and 1 hour and more particularly inclusively between 10 minutes and 40 minutes. The hair is optionally rinsed, preferably rinsed. The fixing composition C is then applied to the hair with a leave-on time preferably inclusively between 1 minutes and 30 hour and more particularly between 3 minutes and 10 minutes. The hair is rinsed and is then optionally shampooed, shampooing preferably being performed, and the hair is then dried.

3). DYEING KIT OF THE INVENTION

A subject of the invention is also a multi-compartment dyeing device or “kit” comprising a first compartment containing a dye composition comprising the composition containing the ingredient i); a second compartment which contains a reducing agent v) as defined previously; the ingredients ii) to iv) as defined previously being divided among the first two compartments, and optionally a third compartment comprising vi) at least one oxidizing agent vii) as defined previously.

According to one variant, the device comprises a first compartment containing a dye composition comprising the composition containing the ingredients i) to iv) as defined previously; a second compartment which contains at least one reducing agent v) as defined previously and optionally a third compartment comprising at least one oxidizing agent vi) and optionally vii) as defined previously.

Alternatively, the dyeing device contains a first compartment containing a dye composition that comprises at least i) a protected-thiol dye, and the ingredients ii) to iv), a second compartment containing an agent capable of deprotecting the protected thiol to liberate the thiol, a third compartment that contains at least one reducing agent v) as defined previously, and optionally a fourth compartment comprising an oxidizing agent vi) and optionally vii) as defined previously.

According to other variants:

-   -   the first compartment contains i) and ii) as defined previously         and the second compartment comprises the ingredients v), iv)         and iii) as defined previously;     -   or alternatively the first compartment contains the ingredients         i), ii) and iii) as defined previously and the second         compartment comprises the ingredients v) and iv);     -   or alternatively the first compartment contains the ingredients         i), iii) and iv) as defined previously and the second         compartment comprises the ingredients v) and ii).

For these variants, a third compartment may be present, which contains an oxidizing agent vi) and optionally vii) as defined previously, and optionally a fourth compartment containing an agent that is capable of deprotecting the protected thiol to liberate the thiol if the ingredient i) of the first compartment is a protected thiol.

Each of the devices mentioned above may be equipped with a means for applying the desired mixture to the hair, for instance the devices described in patent FR 2 586 913.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

The direct thiol, protected thiol or disulfide dyes of formula (I) that are useful in the present invention are known compounds and may be prepared according to methods known to those skilled in the art, especially from the methods described in patent applications EP 1 647 580, EP 2 004 759, WO 2007/110 541, WO 2007/110 540, WO 2007/110 539, WO 2007/110 538, WO 2007/110 537, WO 2007/110 536, WO 2007/110 535, WO 2007/110 534, WO 2007/110 533, WO 2007/110 532, WO 2007/110 531, EP 2 070 988 and WO 2009/040 354.

Examples of Dyeing Concentration of the Starting Materials in Unmodified Form Composition A:

Commercial Ingredient name Supplier Amount Disulfide dye of formula 44 0.5 g % having as counterion the disulfate ion SO₄ ²⁻ (ingredient i)) Cetylstearyl alcohol (50/50 Ecorol 68/50 P Cognis 2.5 g % C₁₆/C₁₈) (ingredient ii)) Myristyl/cetyl/stearyl Crodamol MS- Croda 0.5 g % myristate/palmitate/ PA-(MH) stearate mixture Dipalmitoylethyl- Dehyquart F 30 Cognis 4.5 g % hydroxyethylmethylammonium methosulfate/cetearyl alcohol (ingredients ii) and iii)) Water qs 100%

Composition B

Commercial Ingredient name Supplier Amount Ammonium thioglycolate 71% Ammonium Bruno 20 g % as a 71% aqueous thioglycolate bock solution (pH 6) (ingredient iv)) Diethylenetriamine- Versenex 80 Univar 0.4 g % pentaacetic acid, pentasodium salt as a 40% aqueous solution Fragrance Fresh mint Mane 0.8 g % Monoethanolamine Monoethanolamine Univar 1.21 g % (ingredient v)) Care Oxyethylenated oleyl Brij O20-SO-(MV) Croda 6 g % alcohol (20 OE) (ingredient ii)) Water qs 100%

Composition C

Commercial Ingredient name Supplier Amount Hydrogen peroxide as a H₂O₂ Interox Brenntag 0.48 g % 50% aqueous solution ST-50 (200 vol. aqueous hydrogen peroxide solution) Etidronic acid, Turpinal 4 NL Brenntag 0.02 g % tetrasodium salt, as a 30% aqueous solution Sodium Sodium Merck 0.0035 g % salicylate salicylate Tetrasodium Tetrasodium Penreac 0.004 g % pyrophosphate pyrophosphate decahydrate decahydrate PRS Polydimethyl- Merquat 100 Nalco 0.125 g % diallylammonium chloride at 40% in water Phosphoric acid Prayphos P5 85 Prayon 0.012 g % Crosslinked ethyltrimeth- Salcare SC 95 Ciba 1.3 g % ylammonium methacrylate chloride homopolymer as a 50% inverse emulsion in mineral oil Water qs 100%

9 parts of composition A are mixed with 1 part of composition B in a bowl.

The mixture is applied to brown hair (dark hair having a tone height of 4 (TH4)), with a leave-on time of 20 minutes.

The hair is rinsed.

The fixing formula C is applied to the hair, with a leave-on time of 5 minutes.

The hair is rinsed and is then shampooed, then the hair is dried.

Colorimetric Evaluation Results in the L*a*b* System for Evaluating the Coloring of the Locks:

The color of the locks was evaluated in the L*a*b* system by means of a MINOLTA® CM 3600D spectrocolorimeter (Illuminant D65).

In this L*a*b* system, L* represents the lightness, a* indicates the green/red color axis and b* the blue/yellow color axis. The higher the value of L, the lighter or weaker the color. Conversely, the lower the value of L, the darker or much stronger the color. The higher the value of a*, the redder the shade, and the higher the value of b*, the more yellow the shade.

The variation in coloring between the TH4 dyed and treated locks of hair is measured by (ΔE) according to the following equation:

ΔE=√{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b _(o))²)}{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b _(o))²)}{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b _(o))²)}

In this equation, L*, a* and b* represent the values after treatment, and L_(o)*, a_(o)* and b_(o)* represent the values measured before treatment.

The greater the value of ΔE, the greater the difference in color between the TH4 locks and the uncolored locks.

L* a* b* ΔE* TH4 reference 24.27 3.96 4.72 — After treatment A + B + C 25.1 8.11 8.12 5.43

It is noted that the ΔE value is significantly high after treatment with compositions A+B+C. A mahogany colouration is obtained which is intense and persistent (even after several washing operations).

On the other hand the colour changed very little after the shampooing operations, given the number of successive shampooing operations (even after more than 10 shampooing operations. It is also observed that the coloration is particularly resistant vs. perspiration. 

1-24. (canceled)
 25. A cosmetic composition comprising: i) at least one direct dye chosen from dyes of formula (I) comprising at least one functional group chosen from disulfide, thiol, and protected-thiol functional groups: A-(X)_(p)—C_(sat)—S—U  (I) the salts thereof with an organic or mineral acid, optical or geometric isomers thereof, tautomers thereof, and solvates thereof, wherein: U is a radical chosen from: a) —S—C′_(sat)—(X′)_(p′)-A′; and b) —Y; A and A′, which may be identical or different, are chosen from radicals comprising at least one quaternized cationic chromophore and radicals comprising at least one chromophore bearing a quaternized or quaternizable cationic group; Y is chosen from hydrogen and thiol-function protecting groups; X and X′, which may be identical or different, are chosen from linear or branched, saturated or unsaturated divalent C₁-C₃₀ hydrocarbon-based chains, optionally interrupted and/or optionally terminated at one or both ends with at least one divalent group chosen from: —N(R)—, —N⁺(R)(R)—, —O—, —S—, —CO—, and —SO₂—, wherein R, which may be identical or different, is chosen from hydrogen and C₁-C₄ alkyl, hydroxyalkyl and aminoalkyl radicals; aromatic or non-aromatic, saturated or unsaturated, fused or non-fused (hetero)cyclic radicals optionally comprising at least one identical or different, optionally substituted heteroatom; p and p′, which may be identical or different, are equal to 0 or 1; C_(sat) and C′_(sat), which may be identical or different, are chosen from optionally cyclic, optionally substituted linear or branched C₁-C₁₈ alkylene chains; ii) at least one fatty alcohol chosen from sparingly ethoxylated and non-ethoxylated fatty alcohols; iii) at least one cationic surfactant; iv) at least one alkaline agent; and v) at least one reducing agent.
 26. The composition according to claim 25, wherein the radicals A and/or A′ of the at least one direct dye of formula (I), which may be identical or different, are chosen from radicals comprising at least one quaternized cationic chromophore.
 27. The composition according to claim 25, wherein which the at least one direct dye of formula (I) is a disulfide dye, wherein U is a radical chosen from a) —S—C′_(sat)—(X′)_(p′)-A′.
 28. The composition according to claim 27, wherein the at least one direct dye of formula (I) is a symmetrical disulfide dye of the following formula (Ia): A-(X)_(p)—C_(sat)—S—S—C′_(sat)—(X′)_(p′)-A′  (Ia) wherein A=A′, X=X′, p=p′, and C_(sat)=C′_(sat).
 29. The composition according to claim 25, wherein the at least one direct dye of formula (I) is a dye comprising a thiol or protected-thiol function, wherein U is the radical b) Y, chosen from hydrogen and the following radicals: (C₁-C₄)alkylcarbonyl; (C₁-C₄)alkylthiocarbonyl; (C₁-C₄)alkoxycarbonyl; (C₁-C₄)alkoxythiocarbonyl; (C₁-C₄)alkylthio-thiocarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl; (di)(C₁-C₄)(alkyl)aminothiocarbonyl; arylcarbonyl; aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄)(alkyl)arylaminocarbonyl; carboxyl; SO₃ ⁻M⁺, wherein M⁺ is chosen from alkali metal ions, or alternatively a counterion of the cationic chromophore A and M⁺ are absent; optionally substituted aryl; optionally substituted heteroaryl; optionally cationic, optionally substituted heterocycloalkyl; —C(NR′^(c)R′^(d))═N⁺R′^(e)R′^(f); An′″⁻, wherein R′^(c), R′^(d), R′^(e) and R′^(f), which may be identical or different, are chosen from hydrogen and (C₁-C₄)alkyl groups and An′″⁻ is a counterion; —C(NR′^(c)R′^(d))═NR′^(e); wherein R′^(c), R′^(d) and R′^(e) are defined above; optionally substituted (di)aryl(C₁-C₄)alkyl; optionally substituted (di)heteroaryl(C₁-C₄)alkyl; CR¹R²R³, wherein R¹, R² and R³, which may be identical or different, are chosen from halogen and the following groups: (C₁-C₄)alkyl; (C₁-C₄)alkoxy; optionally substituted aryl; optionally substituted heteroaryl; P(Z¹)R′¹R′²R′³, wherein R′¹ and R′², which may be identical or different, are chosen from hydroxyl, (C₁-C₄)alkoxy and alkyl groups, R′³ is chosen from hydroxyl and (C₁-C₄)alkoxy groups, and Z¹ is chosen from oxygen and sulfur; sterically hindered rings; and optionally substituted alkoxyalkyl.
 30. The composition according to claim 25, wherein, in formula (I), C_(sat) and C′_(sat), which may be identical or different, are chosen from —(CH₂)_(k)— chains, wherein k is an integer ranging from 1 to 8 inclusive.
 31. The composition according to claim 25, wherein, in formula (I), p and p′ are equal to 1, and X and X′, which may be identical or different, are chosen from the following sequence: -(T)_(t)-(Z)_(z)-(T)_(t′)- wherein the sequence is linked in formula (I) symmetrically as follows: C_(sat) (or C′_(sat))-(T)_(t)-(Z)_(z)-(A or A′); wherein: T and T′, which may be identical or different, are chosen from at least one of: —O—; —S—; —N(R)—; —N+(R)(R^(o))—; —S(O)—; —S(O)₂—; —C(O)—; wherein R, R^(o), which may be identical or different, are chosen from hydrogen, C₁-C₄ alkyl radicals, C₁-C₄ hydroxyalkyl radicals and aryl(C₁-C₄)alkyl radicals; and cationic or non-cationic heterocycloalkyl or heteroaryl radicals, optionally monocyclic and optionally comprising two heteroatoms; t and t′, which may be identical or different, are equal to 0 or 1; Z is chosen from: —(CH₂)_(m)—, wherein m is an integer ranging from 1 to 8 inclusive; —(CH₂CH₂O)_(q)— and —(OCH₂CH₂)_(q)—, wherein q is an integer ranging from 1 to 5 inclusive; aryl, alkylaryl and arylalkyl radicals, wherein the alkyl radical is chosen from C₁-C₄ alkyl radicals, optionally substituted with at least one group SO₃M, wherein M is chosen from hydrogen, alkali metals and ammonium groups substituted with at least one radical, which may be identical or different, chosen from linear or branched C₁-C₁₈ alkyl radicals optionally bearing at least one hydroxyl group; and z is 0 or
 1. 32. The composition according to claim 25, wherein the at least one direct dye of formula (I) comprises a chromophore A and optionally a chromophore A′, wherein A and A′ are identical or different and are chosen from the hydrazono cationic chromophores of formulae (II) and (III′), the azo chromophores of formulae (IV) and (IV′) and the diazo chromophores of formula (V) and (V′) below: (*)-Het⁺-C(R^(a))═N—N(R^(b))—Ar,Q⁻  (II) Q⁻,Het⁺-C(R^(a))═N—N(R^(b))—Ar′—(*),  (II′) (*)-Het⁺-N(R^(a))—N═C(R^(b))—Ar,Q⁻  (III) Q⁻,Het⁺-N(R^(a))—N═C(R^(b))—Ar′—(*),  (III′) (*)-Het⁺-N═N—Ar,Q⁻  (IV) Q⁻,Het⁺-N═N—Ar′—(*),  (IV′) (*)—Ar⁺—N═N—Ar″,Q⁻  (V) Ar⁺—N═N—Ar″—(*)  (V′) wherein: Het⁺ is a cationic heteroaryl radical; Ar⁺ is an aryl radical bearing an exocyclic cationic charge; Ar is an optionally substituted aryl group; Ar′ is an optionally substituted divalent (hetero)arylene group; Ar″ is an optionally substituted (hetero)aryl group; R^(a) and R^(b), which may be identical or different, are chosen from hydrogen and optionally substituted (C₁-C₈)alkyl groups; or alternatively the substituent R^(a) with a substituent of Het⁺ and/or R^(b) with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; Q⁻ is an organic or mineral anionic counterion; (*) is the part of the chromophore linked to the rest of the molecule of formula (I).
 33. The composition according to claim 25, wherein the at least one direct dye of formula (I) comprises a chromophore A and optionally a chromophore A′, wherein A and A′ are identical or different and are chosen from: a) the polymethine radicals of formulae (VI) and (VI′) below: W⁺—[C(R^(c))═C(R^(d))]_(m′)—Ar′—(*)Q-  (VI) Ar—[C(R^(d))═C(R^(c))]_(m′)—W′⁺—(*)Q⁻  (VI′) wherein: W⁺ is chosen from cationic heterocyclic and heteroaryl groups; W′⁻ is chosen from divalent heterocyclic and heteroaryl radicals as defined for W⁺; Ar is an optionally substituted aryl group; Ar′ is a divalent aryl radical as defined for Ar; m′ is an integer ranging from 1 to 4 inclusive; R^(c) and R^(d), which may be identical or different, are chosen from hydrogen and optionally substituted (C₁-C₈)alkyl groups, or alternatively R^(c) contiguous with W⁺ or W′⁻ and/or R^(d) contiguous with Ar or Ar′ form, together with the atoms that bear them, a (hetero)cycloalkyl; Q⁻ is an anionic counterion; (*) is the part of the chromophore linked to the rest of the molecule of formula (I); and b) the naphthalimidyl radicals of formula (VII) or (VII′) below:

with

representing the bond with the X or X′, C_(sat) or C′_(sat) group wherein: R^(e), R^(f), R^(g) and R^(h), which may be identical or different, are chosen from hydrogen and optionally substituted (C₁-C₆) alkyl groups.
 34. The composition according to claim 25, wherein the at least one direct dye of formula (I) is a chosen from disulfide dyes of formulae (VIII) to (XIV) and thiol or protected-thiol dyes of formulae (VIII′) to (XIV′) below:

wherein: G and G′, which may be identical or different, are chosen from —NR_(c)R_(d), —NR′_(c)R′_(d) and C₁-C₆ alkoxy groups which are optionally substituted; R¹, R², R³ and R⁴, which may be identical or different, are chosen from hydrogen and (C₁-C₆)alkyl groups; R_(a) and R′_(a), which may be identical or different, are chosen from aryl(C₁-C₄)alkyl groups and C₁-C₆ alkyl groups optionally substituted with a hydroxyl or amino group, C₁-C₄ alkylamino and C₁-C₄ dialkyl amino groups, the alkyl radicals possibly forming, together with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; R_(b) and R′_(b), which may be identical or different, are chosen from hydrogen, aryl(C₁-C₄)alkyl groups and C₁-C₆ alkyl groups that are optionally substituted; R_(c), R′_(c), R_(d) and R′_(d), which may be identical or different, are chosen from hydrogen, aryl(C₁-C₄)alkyl groups, C₁-C₆ alkoxy groups and C₁-C₆ alkyl groups which are optionally substituted; or alternatively two adjacent radicals R_(c) and R_(d), R′_(c) and R′_(d) borne by the same nitrogen atom, together form a heterocyclic or heteroaryl group; R_(e) and R′_(e), which may be identical or different, are chosen from linear or branched C₁-C₆ alkylene and C₂-C₆ alkenylene hydrocarbon-based chains; R_(f) and R′_(f), which may be identical or different, are chosen from di(C₁-C₄)alkylamino, (R″)(R′″)N— groups and quaternary ammonium groups (R″)(R′″)(R″″)N⁺—, wherein R″, R′″ and R″″, which may be identical or different, are chosen from C₁-C₄ alkyl groups or alternatively (R″)(R′″)(R″″)N⁺— is chosen from optionally substituted cationic heteroaryl groups; R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h), R″_(h) and R′″_(h), which may be identical or different, are chosen from hydrogen, halogen atoms, amino, C₁-C₄ alkylamino, C₁-C₄ dialkylamino, cyano, carboxyl, hydroxyl and trifluoromethyl groups, acylamino, C₁-C₄ alkoxy, (poly)hydroxy(C₂-C₄)alkoxy, alkylcarbonyloxy, alkoxycarbonyl and alkylcarbonylamino radicals, acylamino, carbamoyl and alkylsulfonylamino radicals, aminosulfonyl radicals, and C₁-C₁₆ alkyl radicals optionally substituted with a group chosen from C₁-C₁₂ alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino and C₁-C₄ dialkylamino groups, or alternatively two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; or alternatively two groups R_(g) and R′_(g); R″_(g) and R′″_(g), R_(h), and R′_(h); R″_(h) and R′″_(h) borne by two adjacent carbon atoms together form a benzo or indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted with an entity chosen from halogen atoms, amino, C₁-C₄ alkylamino, C₁-C₄ dialkylamino, nitro, cyano, carboxyl, hydroxyl and trifluoromethyl groups, acylamino, C₁-C₄ alkoxy, (poly)hydroxy(C₂-C₄)alkoxy, alkylcarbonyloxy, alkoxycarbonyl and alkylcarbonylamino radicals, acylamino, carbamoyl and alkylsulfonylamino radicals, aminosulfonyl radicals, and C₁-C₁₆ alkyl radicals optionally substituted with a group chosen from C₁-C₁₂ alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino, and C₁-C₄ dialkylamino groups, or alternatively two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; or alternatively two groups R_(i) and R_(g); R′″_(i) and R′″_(g), R′_(i) and R′_(h); and/or R″_(i) and R″_(h) together form a fused (hetero)cycloalkyl; or alternatively when G represents —NR_(c)R_(d) and G′ represents —NR′_(c)R′_(d), two groups R_(c) and R′_(g); R′_(c) and R″_(g); R_(d) and R_(g); R′_(d) and R′″_(g) together form a saturated heteroaryl or heterocycle, optionally substituted with at least one (C₁-C₆)alkyl group; R_(i), R′_(i), R″_(i), and R′″_(i), which may be identical or different, are chosen from hydrogen and C₁-C₄ alkyl groups; R₁, R₂, R₃, R₄, R′₁, R′₂, R′₃ and R′₄, which may be identical or different, are chosen from hydrogen and C₁-C₄ alkyl, C₁-C₁₂ alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino and C₁-C₄ dialkyl amino groups, the alkyl radicals possibly forming, together with the nitrogen atom that bears them, a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; T_(a) and T_(b), which may be identical or different, are chosen from i) a covalent σ bond, ii) at least one radical chosen from —SO₂—, —O—, —S—, —N(R)—, —N⁺(R)(R^(o))—, and —CO—, wherein R, R^(o), which may be identical or different, are chosen from hydrogen, C₁-C₄ alkyl and C₁-C₄ hydroxyalkyl radicals; and aryl(C₁-C₄)alkyl radicals, and iii) cationic or non-cationic, heterocycloalkyl or heteroaryl radicals;

which may be identical or different, are chosen from optionally substituted heterocyclic groups;

is chosen from aryl and heteroaryl groups fused to the imidazolium or phenyl ring; or alternatively is absent from the imidazolium or phenyl ring; m, m′, n and n′, which may be identical or different, are integers ranging from 0 to 6 inclusive, wherein the sums m+n and m′+n′ are equal to integers ranging from 1 to 10 inclusive; Y is chosen from hydrogen and the following protecting groups: (C₁-C₄)alkylcarbonyl; arylcarbonyl; (C₁-C₄)alkoxycarbonyl; aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; 5- or 6-membered cationic monocyclic heteroaryl; 8- to 11-membered cationic bicyclic heteroaryl; cationic heterocycles of the following formula:

—C(NH₂)═N⁺H₂; An′″⁻; wherein An′″⁻ is an anionic counterion; —C(NH₂)═NH; SO₃ ⁻, M⁺, wherein M⁺ is a metal ion; and M′ is an anionic counterion.
 35. The composition according to claim 25, wherein the at least one direct dye of formula (I) is chosen from: the dyes of formulae (XV) to (XV′) below:

wherein in formulae (XV) and (XV′): R and R′″, which may be identical or different, are chosen from hydroxyl, amino (NR_(a)R_(b)) and ammonium (N⁺R_(a)R_(b)R_(c))An⁻ groups; wherein R_(a), R_(b) and R_(c), which may be identical or different, are chosen from hydrogen atom and (C₁-C₄)alkyl groups; or alternatively two alkyl groups R_(a) and R_(b) of the amino or ammonium group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; R′ and R″, which may be identical or different, are chosen from hydrogen and hydroxyl, amino (NR_(a)R_(b)) and ammonium (N⁺R_(a)R_(b)R_(c)) An⁻ groups; R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h), R″_(h) and R′″_(h), which may be identical or different, are chosen from hydrogen, halogen atoms, amino, (di)(C₁-C₄)alkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C₁-C₄ alkoxy, (poly)hydroxy(C₂-C₄)alkoxy, (C₁-C₄)alkylcarbonyloxy, (C₁-C₄)alkoxycarbonyl, (C₁-C₄)alkylcarbonylamino, acylamino, carbamoyl and (C₁-C₄)alkylsulfonylamino groups, aminosulfonyl radicals and (C₁-C₁₆)alkyl radicals optionally substituted with a group chosen from (C₁-C₁₂)alkoxy, hydroxyl, cyano, carboxyl, amino and (di)(C₁-C₄)alkylamino groups, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; R′_(i), R″_(i), R′″_(i) and R″″_(i), which may be identical or different, are chosen from hydrogen and (C₁-C₄)alkyl groups; m and m′, which may be identical or different, are integers ranging from 1 to 10 inclusive; p, p′, q and q′, which may be identical or different, are integers ranging from 1 to 6 inclusive; M′ is an anionic counterion; and Y is chosen from hydrogen and the following protecting groups: (C₁-C₄)alkylcarbonyl; arylcarbonyl; (C₁-C₄)alkoxycarbonyl; aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; 5- or 6-membered cationic monocyclic heteroaryl; 8- to 11-membered cationic bicyclic heteroaryl; cationic heterocycles of following formula:

—C(NH₂)═N⁺H₂ An′″⁻; wherein An′″⁻ is an anionic counterion; —C(NH₂)═NH; and SO₃ ⁻ M⁺, wherein M⁺ is a metal ion; it being understood that when the compound of formula (XV) or (XV′) contains other cationic parts, it is combined with one or more anionic counterions that afford formula (XV) or (XV′) electrical neutrality; and the dyes of formulae (XVI) or (XVI′) below:

wherein in formulae (XVI) and (XVI′): —R₁ is chosen from C₁-C₆ alkyl groups substituted with at least one group chosen from hydroxyl and —C(O)OR′ groups, wherein R′ is chosen from hydrogen, and C₁-C₄ alkyl groups or a group —C(O)—O⁻ and, in the latter case, an anionic counterion An⁻ is absent; R₂ is chosen from C₁-C₆ alkyl groups optionally substituted with at least one hydroxyl group; or alternatively the groups R₁ and R₂ form, together with the nitrogen atom that bears them, a saturated heterocyclic radical substituted with at least one group chosen from hydroxyl, (poly)hydroxy(C₁-C₄)alkyl and/or —C(O)—OR′ groups, wherein R′ is chosen from hydrogen, and C₁-C₄ alkyl groups or a group —C(O)—O⁻ and, in the latter case, an anionic counterion An⁻ is absent; R₃ is chosen from hydrogen and —C(O)OR″ groups, wherein R″ is chosen from hydrogen, alkali metals and C₁-C₆ alkyl groups or alternatively R₃ is a —C(O)—O⁻ group and, in the latter case, an anionic counterion An⁻ is absent; Z is chosen from divalent amido groups —C(O)—N(R)— and —N(R)—C(O)—, and divalent C₁-C₁₀ alkylene groups interrupted with an amido group chosen from —(CH₂)_(n′)—C(O)—N(R)—(CH₂)_(p)— and —(CH₂)_(n″)—N(R)—C(O)—(CH₂)_(p)—, wherein n′ is an integer ranging from 0 to 3 inclusive; p is an integer ranging from 0 to 4 inclusive, n″ is an integer ranging from 0 to 3 inclusive and R is chosen from hydrogen and C₁-C₆ alkyl groups; An⁻ is an anionic counterion; Y is chosen from hydrogen and the following protecting groups: (C₁-C₄)alkylcarbonyl; arylcarbonyl; (C₁-C₄)alkoxycarbonyl; aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; 5- or 6-membered cationic monocyclic heteroaryl; 8- to 11-membered cationic bicyclic heteroaryl; cationic heterocycles of following formula:

—C(NH₂)═N⁺H₂ An′″⁻; wherein An′″⁻ is an anionic counterion; —C(NH₂)═NH; and SO₃ ⁻ M⁺, wherein M⁺ is a metal ion; it being understood that when the compound of formula (XVI) or (XVI′) contains other cationic parts, it is combined with one or more anionic counterions that afford formula (XVI) or (XVI′) electrical neutrality.
 36. The composition according to claim 25, wherein the at least one direct dye of formula (I) is chosen from dyes of the following chemical structures:

wherein An⁻ and M′, which may be identical or different, are anionic counterions.
 37. The composition according to claim 36, wherein An⁻ and M′ are identical and/or are chosen from halides and alkyl sulphates.
 38. The composition according to claim 36, wherein the at least one direct dye of formula (I) is chosen from dyes of formulae 44, 49, 49a and
 55. 39. The composition according to claim 25, wherein ii) the at least one fatty alcohol is a non-ethoxylated fatty alcohol of structure R—OH, wherein R is chosen from saturated or unsaturated, linear or branched radicals comprising from 8 to 40 carbon atoms, optionally substituted with at least one hydroxyl group.
 40. The composition according to claim 39, wherein ii) the at least one fatty alcohol is a non-ethoxylated fatty alcohol chosen from lauryl alcohol, cetyl alcohol, stearyl alcohol, cetylstearyl alcohol, oleyl alcohol, behenyl alcohol, linoleyl alcohol, undecylenyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, myristyl alcohol, and mixtures thereof.
 41. The composition according to claim 25, wherein ii) the at least one fatty alcohol is a sparingly ethoxylated fatty alcohol of the following formula: R^(a)—[O—CH₂—CH₂]_(n)—OH wherein: R^(a) is chosen from linear or branched C₈-C₄₀ alkyl groups and linear or branched C₈-C₄₀ alkenyl groups, optionally substituted with at least one hydroxyl group, and n is an integer ranging from 1 to 6 inclusive.
 42. The composition according to claim 41, wherein ii) the at least one fatty alcohol is chosen from lauryl alcohol containing 2 OE, lauryl alcohol containing 3 OE, decyl alcohol containing 3 OE, decyl alcohol containing 5 OE, stearyl alcohol containing 2 OE, stearyl alcohol containing 3 OE, stearyl alcohol containing 4 OE, stearyl alcohol containing 5 OE, cetyl alcohol containing 2 OE, cetyl alcohol containing 3 OE, cetyl alcohol containing 4 OE and cetyl alcohol containing 5 OE, and mixtures thereof, such as cetearyl alcohol containing 3 OE, cetearyl alcohol containing 4 OE and cetearyl alcohol containing 5 OE.
 43. The composition according to claim 25, wherein iii) the at least one cationic surfactant is chosen from: a) compounds of formula (XVII) below:

wherein in formula (XVII): R₈, R₉, R₁₀ and R₁₁, which may be identical or different, are chosen from linear or branched aliphatic groups comprising from 1 to 30 carbon atoms, and aromatic groups, wherein at least one of the groups R₈, R₉, R₁₀ and R₁₁ comprises from 8 to 30 carbon atoms and the aliphatic groups optionally comprise at least one heteroatom, X⁻ is an anionic counterion; b) compounds of formula (XVIII) below:

wherein in formula (XVIII): R₁₂ is chosen from alkenyl and alkyl groups comprising from 8 to 30 carbon atoms; R₁₃ is chosen from hydrogen, C₁-C₄ alkyl groups and alkenyl and alkyl groups comprising from 8 to 30 carbon atoms; R₁₄ is chosen from C₁-C₄ alkyl groups; R₁₅ is chosen from hydrogen and C₁-C₄ alkyl groups; X⁻ is anionic counterion; c) compounds of formula (XIX) below:

wherein in formula (XIX): R₁₆ is chosen from alkyl groups comprising from about 16 to 30 carbon atoms, which may be optionally hydroxylated and/or interrupted with at least one oxygen atom; R₁₇ is chosen from hydrogen, alkyl groups comprising from 1 to 4 carbon atoms and —(CH₂)₃—N⁺(R_(16a))(R_(17a))(R_(18a)), wherein R_(16a), R_(17a), R_(18a), which may be identical or different, are chosen from hydrogen and alkyl groups comprising from 1 to 4 carbon atoms; R₁₈, R₁₉, R₂₀ and R₂₁, which may be identical or different, are chosen from hydrogen and alkyl groups comprising from 1 to 4 carbon atoms, and X⁻ is an anionic counterion; d) compounds of formula (XX) below:

wherein in formula (XX): R₂₂ is chosen from C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl and C₁-C₆ dihydroxyalkyl groups; R₂₃ is chosen from: the group

linear or branched, saturated or unsaturated C₁-C₂₂ hydrocarbon-based groups R₂₇, hydrogen; R₂₅ is chosen from: the group

linear or branched, saturated or unsaturated C₁-C₆ hydrocarbon-based groups R₂₉, hydrogen; R₂₄, R₂₆ and R₂₈, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C₇-C₂₁ hydrocarbon-based groups; r, s and t, which may be identical or different, are integers ranging from 2 to 6 inclusive; r1 and t1, which may be identical or different, are equal to 0 or 1, wherein r2+r1=2r and t1+t2=2t, y is an integer ranging from 1 to 10 inclusive; x and z, which may be identical or different, are integers ranging from 0 to 10 inclusive; X⁻ is an organic or inorganic anionic counterion; with the proviso that the sum x+y+z ranges from 1 to 15 inclusive, that when x is 0, then R₂₃ denotes R₂₇ and that when z is 0, then R₂₅ denotes R₂₉.
 44. The composition according to claim 43, wherein iii) the at least one cationic surfactant is chosen from cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof.
 45. The composition according to claim 25, wherein iv) the at least one alkaline agent is chosen from aqueous ammonia, alkali metal carbonates and bicarbonates, alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (XXI) below:

wherein: W is chosen from divalent C₁-C₆ alkylene radicals optionally substituted with a radical chosen from hydroxyl and C₁-C₆ alkyl radicals, and/or optionally interrupted with at least one heteroatom chosen from oxygen and NR^(u); R^(x), R^(y), R^(z) R^(t) and R^(u), which may be identical or different, are chosen from hydrogen and C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl and C₁-C₆ aminoalkyl radicals.
 46. The composition according to claim 25, wherein v) the at least one reducing agent is chosen from thioglycolic acid, thiolactic acid, 3-mercaptopropionic acid, thiomalic acid, 2,3-dimercaptosuccinic acid, cysteine, N-glycyl-L-cysteine, L-cysteinylglycine and esters and salts thereof, thioglycerol, cysteamine and C₁-C₄ acyl derivatives thereof, N-mesylcysteamine, N-acetylcysteine, N-(mercapto-2-ethyl) gluconamide, pantetheine, N-(mercaptoalkyl)-ω-hydroxyalkylamides, N-mono- or N,N-dialkylmercapto-4-butyramides, aminomercaptoalkyl amides, N-(mercaptoalkyl)succinamic acids and N-(mercaptoalkyl)succinimides, alkylamino mercaptoalkyl amides, the azeotropic mixture of 2-hydroxypropyl thioglycolate and of (2-hydroxy-1-methyl)ethyl thioglycolate, mercaptoalkylamino amides, and N-mercaptoalkylalkanediamides.
 47. A method for dyeing and/or lightening keratin fibers, comprising applying to the keratin fibers: i) at least one dye of formula (I) according to claim 25; ii) at least one fatty alcohol; iii) at least one cationic surfactant; iv) at least one alkaline agent v) at least one reducing agent; vi) optionally at least one chemical oxidizing agent; and vii) optionally at least one organic thickening polymer; wherein the ingredients i) to vii) are applied to the keratin fibers either together or separately.
 48. The method according to claim 47, wherein a composition according to claim 25 is applied to the keratinous fibers.
 49. The method according to claim 47, comprising applying to the keratin fibers a reducing composition comprising iv) at least one alkaline agent, v) at least one reducing agent and optionally ii) at least one fatty alcohol, followed by the application of a dye composition comprising i) at least one direct dye of formula (I), ii) at least one fatty alcohol and iii) at least one cationic surfactant.
 50. The method according to claim 47, wherein the keratin fibers are dark keratin fibers having a tone depth of less than or equal to 6, and wherein the at least one direct dye of formula (I) is chosen from: dyes of formulae (XIII), (XIII′), (XIV), and (XIV′), as defined in claim 34; and dyes of formulae (XV), (XV′), (XVI), and (XVI′), as defined in claim
 35. 51. The method according to claim 50, wherein the at least one direct dye of formula (I) is chosen from dyes of the following chemical structures:


52. A multi-compartment device or kit for dyeing keratin fibers comprising: a first compartment comprising a dye composition comprising i) at least one direct dye of formula (I) according to claim 25; a second compartment comprising at least one reducing agent v); and optionally, a third compartment comprising vi) at least one chemical oxidizing agent; wherein the first and/or second compartment further comprises ii) at least one fatty alcohol, iii) at least one cationic surfactant, and/or iv) at least one alkaline agent. 